CN106118644B - A kind of hydridization skeleton borate prepares the method and its application of carbon quantum dot material - Google Patents
A kind of hydridization skeleton borate prepares the method and its application of carbon quantum dot material Download PDFInfo
- Publication number
- CN106118644B CN106118644B CN201610424440.9A CN201610424440A CN106118644B CN 106118644 B CN106118644 B CN 106118644B CN 201610424440 A CN201610424440 A CN 201610424440A CN 106118644 B CN106118644 B CN 106118644B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- carbon quantum
- borate
- carbon
- prepares
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
Abstract
The invention discloses the method and its application that a kind of hydridization skeleton borate prepares carbon quantum dot material, belong to carbon quantum dot preparing technical field.The present invention relates to the preparation of borate, borates to prepare the method for carbon quantum dot, some carbon quantum dot Fluorescent Characterizations, UV, visible light detection and detection to special metal salt.The material obtains crystal using hydro-thermal reaction, and carbon quantum dot is obtained after heating to it.The molecular formula of borate is C2H9N2B5O9Cd, space group P21/ n, cell parameter α=90 °, β=90.659 (5) °, γ=90 °, Z=4, unit-cell volume The carbon dots material has good application prospect in fields such as biomarker, positioning, fluorescence, tracer, specific ion detection, sensings.
Description
Technical field
The invention belongs to carbon quantum dot preparing technical field, more particularly to a kind of hydridization skeleton borate prepares carbon quantum dot
The method and its application of material.
Background technology
Carbon quantum dot (carbon dots) is a kind of size in 10nm discrete torispherical carbon nano-particles new materials below, is tool
The quanta point material for having chemical inertness, photostability, hypotoxicity and good biocompatibility is examined in bio-imaging and labeled analysis
The fields such as survey, opto-electronic conversion and catalysis show huge application prospect, therefore have attracted numerous researchers in synthesizing mean
With the various trials and exploration in carbon source selection.
In general, the customary preparation methods of carbon dots have method from top to bottom：It is formed or is removed from big carbon structure material
Go out carbon dots, and method from bottom to top：Carbon dots come from the other predecessor of molecular level；According to the origin classification of carbon, carbon dots can be divided into organic
Or prepared by inorganic carbon source.Different synthesizing means and carbon source is to determine the structures such as the carbon core size, terminal functionality, doping of carbon dots
The key of feature, and then influence whether property and the application of carbon dots.If hydro-thermal prepares nanometer carbon dots, it can get and grown not on end group
The carbon dots of same functional group's (hydroxyl, carbonyl and carboxyl etc.) or the different elements of doping, and the luminous intensity of carbon dots can be improved or urged
Change efficiency；The step of pyrolysis, microwave, the methods of calcining synthesis carbon quantum dot, is fairly simple, can get uncommon lipophile carbon
Point；But the carbon quantum dot handled by high temperature pyrolysis, it causes that the reunion of itself occurs between carbon quantum dot sometimes, makes
It is uneven to obtain its Size Distribution.For the carbon dots prepared under different condition there are larger surface texture difference, this otherness can be tight
A variety of properties such as the ultraviolet of carbon dots, fluorescence, catalysis, bioactivity are influenced again.
Currently using duct compound such as zeolite, mesoporous material, microporous phosphate etc. as template, carbon Nano quantum is synthesized
Point (carbon dots) material is emerging research hotspot.These templates have not only acted as the effect for fixing carbon source and product in the reaction,
Also there is important influence to the pattern of the carbon quantum dot finally prepared, size, by selecting different templates, is expected to obtain more
The carbon dots material of superperformance, to meet its application in different field.Correspondingly, we are by selecting hydridization skeleton boron
Hydrochlorate crystalline material prepares carbon dots material as template；The carbon dots prepared inside borate crystal, growth environment are similar
In microporous phosphate, carbon source comes from the organic amine of itself, and carbon dots growing environment is in the lattice of strictly monotone, proper alignment
In, provide exploration thinking to obtain the uniform carbon dots of surface topography.
Invention content
To overcome above-mentioned shortcoming and deficiency existing in the prior art, the primary purpose of the present invention is that providing a kind of hydridization
Skeleton borate.
Another object of the present invention is to provide the preparation methods of above-mentioned hydridization skeleton borate.
Another object of the present invention is to provide the methods that above-mentioned hydridization skeleton borate prepares carbon quantum dot material.
Another object of the present invention is to provide the carbon quantum dot materials that the above method prepares.
It is still another object of the present invention to provide the applications of above-mentioned carbon quantum dot material.
The purpose of the invention is achieved by the following technical solution：A kind of hydridization skeleton borate material, the compound molecule
Formula C2H9N2B5O9Cd, more specifically [C2N2H8][CdB5O8(OH)], space group P21/ n, cell parameter α=90 °, β=90.659 (5) °, γ=90 °, Z
=4, unit-cell volumeInclude an ethylenediamine molecule, a cadmium in the structural unit of the compound
Atom, a five core boron oxygen cluster units.
The preparation method of above-mentioned hydridization skeleton borate material, includes the following steps：Weigh 0.1860-0.5580g boron
Acid (H3BO3), 0.0244-0.1709g zinc oxide (ZnO), 0.0878-0.2196g cadmium hydroxides (Cd (OH)2) it is added to 28ml high
It presses in reaction kettle, then measures with pipette the N-N- dimethylformamides (DMF) of the ethylenediamine (en) of 1-10ml, 1-10ml respectively
It is added in the reaction kettle；Its molar ratio is 1~3：0.1~0.7：0.2~0.5：4.9~49：4.3~43, mixture stirring
Dress kettle, which is put into drying box, after device stirs 10-50 minutes is heated to 100-250 DEG C, reacts 0.5-7 days, it is naturally cold to turn off drying box
But room temperature is arrived, the granular crystals hydridization skeleton borate material of water white transparency is obtained after opening kettle.
A kind of method that hydridization skeleton borate prepares carbon quantum dot material, includes the following steps：By drying at room temperature
Hydridization skeleton borate material, is put into resistance furnace, with the heating rate of 1-50 DEG C/min, by hydridization skeleton borate material from room
It is started to warm up under temperature, was heated to 200-600 DEG C by 60-200 minutes respectively, then distinguished at such a temperature after constant temperature 1-4 hours
It is slowly cooled to room temperature, is ground up, sieved, then is washed with ethyl alcohol, most obtains carbon quantum dot through spin dialysis afterwards.
A kind of carbon quantum dot material is prepared by the above method.Through different temperatures 200-600 in the method for above-mentioned preparation
It can obtain obviously not reuniting each other after DEG C calcination processing, with the carbon quantum dot in the majority of hexagon, and carbon quantum dot
Size relatively, and can see apparent lattice fringe.
The application of carbon quantum prepared by above-mentioned hydridization skeleton borate, in the solution with the increase of hydrochloric acid infusion volume,
Its fluorescence intensity gradually increases, and shows that the presence of micro hydrochloric acid plays the role of enhancing to the fluorescence of carbon dots, can respond Acid-Base strengths,
It can be applied to Acid-Base strengths indicator.
The application of carbon quantum prepared by above-mentioned hydridization skeleton borate can be used to detect cesium ion micro in water and again
Metal chromium ions have potential value in terms of water quality monitoring.
The application of carbon quantum prepared by above-mentioned hydridization skeleton borate, it is glimmering to carbon quantum dot according to CdSe/ZnS quantum dots
Photoresponse situation may be used to determine CdSe/ZnS quantum dots.
The purposes of carbon quantum prepared by above-mentioned hydridization skeleton borate, in biomarker, positioning, fluorescence, tracer, specific
The fields such as ion detection, sensing have a good application prospect.
The present invention has the following advantages and effects with respect to the prior art：
Organic borate provided by the invention is the crystal grown in solvent process for thermosynthesizing.Used material preparation
It is simple for process, yield is high and reproducible.
The advantages of borate is a kind of novel hydridization skeleton borate crystal material, the material is that carbon source comes from hydridization
The organic component of borate, carbon dots growing environment are in the lattice of strictly monotone, proper alignment, so as to obtain surface topography
Uniform carbon dots.
The invention is not only to design and develop the borate of novel structure to provide the thinking of science, more prepare property with
The carbon dots material that structure change is mutually coordinated provides feasible Research approach.
Description of the drawings
Fig. 1 is a, b, c after different temperatures calcining, the transmission electron microscope picture of d samples.
Fig. 2 is the unprocessed of compound and a after different temperatures is calcined, b, c, the infrared figure of d samples.
Fig. 3 is experiment and the theory PXRD figures of the unprocessed of compound and the sample by different temperatures calcining.
Fig. 4 is a after treatment of different temperature, b, c, the UV absorption spectrogram of d samples.
Fig. 5 is a after treatment of different temperature, b, c, the EPR spectrograms of d samples.
Fig. 6 is a, b, c after different temperatures calcining, the XPS spectrum figure of d samples.
Fig. 7 is a by different heat treatment, b, c, fluorogram of the d samples under different excitation wavelengths.
Fig. 8 is the titration with hydrochloric acid fluorogram of a samples；Arrow indicates that volume is ascending wherein in figure.
Fig. 9 is influence result figure of the variation to the fluorescence intensity of sample of Gold Samples category ion concentration；It is a samples to scheme a
Chromium nitrate solution, figure b are the cesium chloride solution of a samples, and figure c is the chromium nitrate solution of d samples, and figure d is that the cesium chloride of d samples is molten
Liquid；Arrow indicates that volume is ascending wherein in figure.
Figure 10 is influence result figure of the variation to the fluorescence intensity of sample of quantum dot concentration in sample；It is in a samples to scheme a
CsPbBr is added3Quantum dot, figure b are that CdSe/ZnS quantum dots are added in a samples, and figure c is that CsPbBr is added in d samples3Quantum
Point, figure d are that CdSe/ZnS quantum dots are added in d samples；Arrow indicates that volume is ascending wherein in figure.
Figure 11 is the fluorogram of different solvents d samples.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
The preparation of 1 compound of embodiment
Weigh boric acid (H3BO3) 0.1860 to 0.5580g, zinc oxide (ZnO) 0.0244 arrive 0.1709g, cadmium hydroxide (Cd
(OH) it 2) 0.0878 to 0.2196g is added in 28ml autoclaves, then measures the ethylenediamine of 1-10ml respectively with pipette
(en), the N-N- dimethylformamides (DMF) of 1-10ml are added in the reaction kettle；Its molar ratio is 1-3：0.1-0.7：0.2-
0.5：4.9-49：4.3-43, dress kettle is put into drying box after mixture is stirred 5-60 minutes with the constant temperature blender with magnetic force with rotor
In be warming up at 100-250 DEG C and react 0.5-7 days, turn off drying box and naturally cool to room temperature, crystal can be obtained；Through X-ray
Single crystal diffraction is analyzed, and determines that the crystal is C2H9N2B5O9Cd.The material mol ratio of specific reactant embodiment is as follows：
(1)H3BO3：Zn(OH)2：Cd(OH)2：en:DMF=1：0.1：0.2：4.9：4.3
(2)H3BO3：Zn(OH)2：Cd(OH)2：en:DMF=3：0.7：0.5：49：43
(3)H3BO3：Zn(OH)2：Cd(OH)2：en:DMF=1：0.1：0.5：49：43
(4)H3BO3：Zn(OH)2：Cd(OH)2：en:DMF=3：0.7：0.2：4.9：4.3
(5)H3BO3：Zn(OH)2：Cd(OH)2：en:DMF=1：0.1：0.2：49：43
(6)H3BO3：Zn(OH)2：Cd(OH)2：en:DMF=3：0.7：0.5：4.9：4.3
(7)H3BO3：Zn(OH)2：Cd(OH)2：en:DMF=1：0.1：0.2：4.9：43
(8)H3BO3：Zn(OH)2：Cd(OH)2：en:DMF=3：0.7：0.5：49：4.3
(9)H3BO3：Zn(OH)2：Cd(OH)2：en:DMF=1：0.7：0.5：49：43
(10)H3BO3：Zn(OH)2：Cd(OH)2：en:DMF=3：0.1：0.2：4.9：4.3
Select the suitable crystal of size under the microscope, by diffractometer, select Cu Ka rays (λ=
It is 0.071073nm) that radiation source tests crystal and collect diffraction data, then to the diffraction data of collection absorb and test
Card.Directly crystal is parsed with program, theoretical plus hydrogen mode is taken to carry out adding hydrogen to C, N, O.Finally, using complete matrix
Least square method carries out refine to the coordinate and anisotropic parameters of all non-hydrogen atoms.The result shows that the crystal is monoclinic crystal
System, space group P21/ n, cell parameter α=
90 °, β=90.659 (5) °, γ=90 °, Z=4, unit-cell volume
The preparation of 2 carbon quantum dot of embodiment
By sample (C dry at room temperature2H9N2B5O9Cd) it is divided into quarter, is respectively put into resistance furnace, with 1-50 DEG C/min
Heating rate sample is started to warm up from 25 DEG C at room temperature, respectively pass through 50-150 minute, 150-200 minutes, 100-200 divide
Clock and it is heated within 150-200 minutes 250-350 DEG C, 350-450 DEG C, 450-550 DEG C, 500-600 DEG C, then respectively at such a temperature
Constant temperature is slowly cooled to room temperature after four hours, obtains sample and names a, b, c, d respectively；It is washed with ethyl alcohol after being ground up, sieved,
Carbon dots most are obtained through spin dialysis afterwards, then obtain the carbon dots shape appearance figure under different temperatures, such as Fig. 1 through transmission electron microscope.
Embodiment 3 is infrared and XRD is detected
Fig. 2 be do not do any processing sample and the sample after different temperatures is calcined do infrared spectrum.Untreated sample
In 1600cm in the general figure of product-1There is more sharp absorption peak at place, is C-NH2Characteristic peak, and after being calcined by different temperatures,
It fades away at the peak.Showing the raising with calcination temperature, some functional groups in compound gradually lose, and compound
A degree of cave in has occurred in crystal structure.Fig. 3 is the X-ray powder diffraction spectrogram of sample after heat treatment, which shows
Information it is similar to infrared spectrum.Infrared and X-ray powder diffraction spectrogram presence, further demonstrates in ultraviolet spectra
Some results reliability.
The ultraviolet test of 4 carbon dots of embodiment
It is respectively that 0.1-0.5g is added in small beaker, then respectively addition 1-10ml is anhydrous to weigh above-mentioned a, b, c, d sample
Ethyl alcohol dissolves simultaneously magnetic agitation 10-30 minutes, and a period of time is stood after 10-30 minutes ultrasonic.Measure 1-5ml supernatant liquids into
Row test, test scope are 190~800nm.The ultraviolet absorption spectrum of four kinds of samples such as Fig. 4, there is very strong suction near 220nm
Peak is received, the peak is caused by the π between carbon-coating in carbon dots-pi-electron transition, and with the raising of calcination temperature, which has occurred bright
Aobvious blue shift.A, have wider absorption peak at 350nm in the spectrogram of b, c sample, be carbon dots in outermost carbon phase even-
NH2Or the characteristic peak of-NH-R groups.With the raising of heat treatment temperature, the weakened at the peak shows C-NH2Or C-
NH-R groups are gradually being sloughed, and the peak disappears in d, explanation-NH2Either-NH-R groups are basic or all slough.This is existing
Carbon radicals may be all produced as showing in four kinds of samples.
Embodiment 5 EPR analyses
It is respectively 0.01-0.05g to weigh a, b, c, d sample, and four kinds of samples are fitted into nuclear magnetic tube, total with electron paramagnetic
Vibration wave spectrometer is tested and collects data.As shown in figure 5, in 3520mT or so there is absorption peak on EPR collection of illustrative plates, (the g factors are about
For 1.995), this demonstrate single electron free radical is produced in the sample after Overheating Treatment, this single electron free radical comes from
The sp that carbon dots end group is not coordinated completely2Hydbridized carbon atoms, this phenomenon further demonstrate the presence of carbon dots.In addition with heat
The EPR intensity of the raising of the temperature of processing, sample enhances therewith, the reason is that-the NH in sample on the outermost carbon of carbon quantum dot2
Or-NH-R groups are gradually sloughed with the raising of heat treatment temperature, the carbon radicals generated in sample slowly increase, to
The EPR intensity of sample enhances therewith.
Embodiment 6 XPS tests
Fig. 6 is the XPS spectrum figure of sample it is found that Fig. 6 wherein a, b, c, d have peak, the peak position of O1s to exist in C1s in 284.6eV
526eV, it is consistent with the peak position of graphitic carbon, and O1s peak intensity ratio C1s high, show that the carbon dots generated in four kinds of samples are oxygen
Graphite carbon.
7 carbon dots fluorometric investigation of embodiment
This test uses the four kinds of samples handled well in ultraviolet-visible spectrum analysis.The clear of 1-3ml is measured respectively
Clear liquid is fitted into cuvette, and fluorometric investigation is carried out to sample using Fluorescence Spectrometer.It is visited when test by changing excitation wavelength
Study carefully influence of the different excitation wavelengths to fluorescent.From fluorogram Fig. 7 of four kinds of samples, four kinds of samples have preferably
Photoluminescent property.Other than the excitation wavelength of d samples is 290nm, the excitation wavelength of remaining sample is all 320nm.With other three
Kind sample is compared, and the photoluminescent property of the sample is relatively less better.Structure shows that different calcination temperatures can be to the fluorescence of carbon dots
Property affects.
8 titration with hydrochloric acid of embodiment
Configuration 5 × 10-4The hydrochloric acid solution of mol/L is used as titrating solution, and d samples is selected to be tested, and measures 3ml ultraviolet-visibles
Slowly hydrochloric acid is added dropwise to it in the sample liquid handled well in spectrum analysis, and the volume of dropwise addition is 20-320 μ L.Fig. 8 drips for hydrochloric acid
The fluorogram of random sample product, under the excitation of 320nm, with the increase of hydrochloric acid infusion volume, fluorescence intensity gradually increases, and shows micro-
The presence of amount hydrochloric acid plays the role of enhancing to the fluorescence of carbon dots.
9 metal ion of embodiment titrates
Metal ion chooses cesium chloride and chromic nitrate, takes clear liquid to test after a and d samples are dissolved in ethyl alcohol.Configuration
The chromium nitrate aqueous solution of 0.001mol/L, the sample for measuring 3ml are fitted into cuvette, glimmering to not adding the sample of metal ion to carry out
Optical tests.The liquid-transfering gun for being 5~50 microlitres with range is added metal ion solution and is tested one by one one by one.Nitre in a samples
The addition of sour chromium solution is respectively：10-100 μ L (10 μ L indicate that the total amount that chromium nitrate solution in cuvette is added is 10 μ L), d
The addition of chromium nitrate solution is respectively in sample：5-200μL.The operation same chromic nitrate of cesium chloride solution is added in a samples
Volume is respectively that the volume being added in 20-1700 μ L, d samples is respectively 5-200 μ L.The excitation wavelength chosen when test is all
320nm obtains the fluorescence titration figure of the metal ion of a and d samples.As shown in Fig. 9-a, Cr3+To the carbon quantum dot in sample
There are apparent turn on effects, with the increase of nitric acid chromium concn, the fluorescence intensity of sample gradually increases.The result of Fig. 9-c is just
Well on the contrary, Cr3+There are apparent turn off effects to the carbon quantum dot in sample, with the increase of nitric acid chromium concn, sample
Fluorescence intensity gradually weakens.Same sample is after different temperatures calcining, the fluorescence of sample under the titration of identical metal ion
Property is completely on the contrary, this occurs in carbon dots or for the first time.Cs in Fig. 9-b+There are turn on effects to the carbon quantum dot in sample
It answers, with the increase of cesium chloride solution concentration, the fluorescence intensity of sample gradually increases.Same Fig. 9-the b of result of Fig. 9-d.Micro
Carbon dots are in micro chromic nitrate and cesium chloride (10-9Mol ranks) in the presence of, the fluorescence intensity of carbon dots changes significantly, and shows
The carbon quantum dot of preparation can be used for detecting cesium ion micro in water and heavy metal chromium ion, have in terms of water quality monitoring latent
Value.
10 quantum dot of embodiment titrates
Choose water-soluble CdSe/ZnS quantum dot and oil-soluble (toluene solvant) CsPbBr3Quantum dot makees titrating solution, configuration
Concentration be respectively 4 × 10-3Mg/mL and 5 × 10-3Mg/mL, with being dissolved in a samples after ethyl alcohol and be dissolved in toluene and water respectively
D samples are tested.CsPbBr in a samples3The volume that quantum dot titrating solution is added is respectively in 20-1200 μ L, d samples
CsPbBr3The volume that quantum dot titrating solution is added is respectively 10-600 μ L.CdSe/ZnS quantum dots titrating solution is added in a samples
Volume is respectively that the volume that CdSe/ZnS quantum dot titrating solutions are added in 20-1500 μ L, d samples is respectively 10-700 μ L.Fluorescence
Spectrogram is as shown in Figure 10, and the excitation wavelength that when test is chosen all is 320nm.By Figure 10-a it is found that with CsPbBr3Quantum dot by
It is gradually added, the fluorescence intensity of sample slowly dies down, and shows CsPbBr3There is mutual quenching between quantum dot and carbon quantum dot obtained
Effect, the same to Figure 10-a of result of Figure 10-c.From Figure 10-b it is found that with CdSe/ZnS quantum dot concentration increase, sample
The fluorescence intensity of middle carbon quantum dot gradually increases, and has small peak appearance at 527nm, is the characteristic peak of CdSe/ZnS quantum dots,
For CdSe/ZnS.
11 different solvents of embodiment influence the photoluminescent property of d samples
In Fig. 10, the fluorescence intensity of figure a and b is significantly different.In fig. 11, water, ethyl alcohol and toluene is used to dissolve d samples respectively
Product, as a result as shown in the figure.The fluorescent intensity for being dissolved in water is minimum, is dissolved in the fluorescence intensity highest of the sample of toluene, shows d samples
Carbon dots in product are oil-soluble carbon dots.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (8)
1. a kind of hydridization skeleton borate material, it is characterised in that：The hydridization skeleton borate material compound molecule formula
C2H9N2B5O9Cd, space group P21/ n, cell parameter α=90 °, β=90.659 (5) °, γ=90 °, Z=4, unit-cell volume
The preparation method of the hydridization skeleton borate material, includes the following steps：Weigh 0.1860-0.5580g boric acid,
0.0244-0.1709g zinc oxide, 0.0878-0.2196g cadmium oxides are added in 28ml autoclaves, then are distinguished with pipette
The N-N- dimethylformamides of the ethylenediamine, 1-10ml that measure 1-10ml are added in the reaction kettle；Its molar ratio is 1-3：0.1-
0.7：0.2-0.5：4.9-49：4.3-43, dress kettle, which is put into drying box, after mixture is stirred 10-50 minutes with blender is heated to
It 100-250 DEG C, reacts 0.5-7 days, turns off drying box and naturally cool to room temperature, the granular crystals of water white transparency are obtained after opening kettle
Hydridization skeleton borate material.
2. the method that hydridization skeleton borate described in claim 1 prepares carbon quantum dot material, it is characterised in that：Including following
Step：By hydridization skeleton borate material dry at room temperature, it is put into resistance furnace, it, will be miscellaneous with the heating rate of 1-50 DEG C/min
Change skeleton borate material from starting to warm up at room temperature, is heated to 200-600 DEG C by 60-200 minutes respectively, then respectively at this
At a temperature of constant temperature be slowly cooled to room temperature after 1-4 hours, be ground up, sieved, then washed with ethyl alcohol, most obtain carbon through spin dialysis afterwards
Quantum dot.
3. a kind of carbon quantum dot material is prepared by the method described in claim 2.
4. the application for the carbon quantum dot material that the method described in claim 2 prepares, it is characterised in that：It is strong applied to soda acid
Spend indicator.
5. the application for the carbon quantum dot material that the method described in claim 2 prepares, it is characterised in that：In water quality monitoring side
Face is applied to cesium ion and heavy metal chromium ion micro in detection water.
6. the application for the carbon quantum dot material that the method described in claim 2 prepares, it is characterised in that：According to CdSe/ZnS
Quantum dot may be used to determine CdSe/ZnS quantum dots to carbon quantum dot fluorescence response situation.
7. the application for the carbon quantum dot material that the method described in claim 2 prepares, it is characterised in that：According to CsPbBr3Amount
Son point may be used to determine CsPbBr to carbon quantum dot fluorescence response situation3Quantum dot.
8. the application for the carbon quantum dot material that the method described in claim 2 prepares, it is characterised in that：Biomarker,
Positioning, fluorescence, tracer, specific ion detection and sensory field application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610424440.9A CN106118644B (en) | 2016-06-14 | 2016-06-14 | A kind of hydridization skeleton borate prepares the method and its application of carbon quantum dot material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610424440.9A CN106118644B (en) | 2016-06-14 | 2016-06-14 | A kind of hydridization skeleton borate prepares the method and its application of carbon quantum dot material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106118644A CN106118644A (en) | 2016-11-16 |
| CN106118644B true CN106118644B (en) | 2018-11-02 |
Family
ID=57469621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610424440.9A Expired - Fee Related CN106118644B (en) | 2016-06-14 | 2016-06-14 | A kind of hydridization skeleton borate prepares the method and its application of carbon quantum dot material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106118644B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8252256B2 (en) * | 2012-01-01 | 2012-08-28 | King Abdulaziz City for Science and Technology (KACST) | Synthesis of zinc-oxide nanoparticles and their use for photo catalytic degradation of cyanide |
| CN103059833A (en) * | 2012-11-08 | 2013-04-24 | 广东工业大学 | Organic amine template borate fluorescent material as well as preparation method and application thereof |
| CN105339301A (en) * | 2013-05-02 | 2016-02-17 | 威廉马歇莱思大学 | Methods of producing graphene quantum dots from coal and coke |
| CN103642494A (en) * | 2013-12-27 | 2014-03-19 | 中国科学院上海微***与信息技术研究所 | Preparation method for fluorescence carbon-based quantum dot |
-
2016
- 2016-06-14 CN CN201610424440.9A patent/CN106118644B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106118644A (en) | 2016-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shu et al. | Incorporation of perovskite nanocrystals into lanthanide metal-organic frameworks with enhanced stability for ratiometric and visual sensing of mercury in aqueous solution | |
| CN108440580A (en) | A kind of Zn5The preparation method of cluster Base Metal-organic framework materials and its modified material | |
| CN107603592B (en) | Preparation method of magnetic fluorescent nano material and fluorescence detection method thereof | |
| CN101531401B (en) | Preparation method of MoO3 nanorod powder with sensitive photochromic property | |
| Cao et al. | A novel method for the preparation of solvent-free, microwave-assisted and nitrogen-doped carbon dots as fluorescent probes for chromium (VI) detection and bioimaging | |
| CN106957646B (en) | A kind of gallate long-persistence nano-luminescent materials and its preparation method and application | |
| Gómez et al. | Dehydroxylation and the crystalline phases in sol-gel zirconia | |
| Shi et al. | An anionic layered europium (iii) coordination polymer for solvent-dependent selective luminescence sensing of Fe 3+ and Cu 2+ ions and latent fingerprint detection | |
| Zhang et al. | Monodisperse lanthanide oxyfluorides LnOF (Ln= Y, La, Pr–Tm): morphology controlled synthesis, up-conversion luminescence and in vitro cell imaging | |
| Xi et al. | Comparison of upconversion luminescent properties and temperature sensing behaviors of β-NaYF 4: Yb 3+/Er 3+ nano/microcrystals prepared by various synthetic methods | |
| CN115092958A (en) | Chiral bismuth oxyhalide two-dimensional material and preparation method thereof | |
| CN104818015A (en) | Picolinic acid dissimilar metal organic framework light-emitting material and synthesis method thereof | |
| CN106118644B (en) | A kind of hydridization skeleton borate prepares the method and its application of carbon quantum dot material | |
| CN103028738B (en) | Method for controllably preparing FeNi3 micro-nano materials in various shapes | |
| Gong et al. | Template-free hydrothermal synthesis and luminescent properties of octahedral NaGd (MoO4) 2: Eu3+ microcrystals | |
| Wang et al. | Single-crystalline CuGeO3 nanorods: Synthesis, characterization and properties | |
| CN106986374A (en) | A kind of high specific surface area and mesoporous zinc-oxide nano cluster and preparation method thereof | |
| CN102259935A (en) | Auxiliary hydro-thermal method for preparing bird-nest-shaped Co3O4 surfactant | |
| Ma et al. | Ratiometric fluorescent nanosensor based on carbon dots for the detection of mercury ion | |
| Chen et al. | Water‐Soluble, Monodisperse, Lanthanide‐Doped Y (Gd) VO4 Nanocrystals as Promising Multimodal Bioprobe | |
| Dong et al. | Increasing doping solubility of RE3+ ions in fergusonite BiVO4 via pressure-induced phase transition | |
| CN102220638B (en) | Preparation method of cubic iron trioxide monocrystal | |
| CN109054036A (en) | Sandwich type manganese coordination polymer, preparation method and its application in cation detection of blue-green fluorescent | |
| Zhao et al. | Synthesis and Pressure‐induced Reversible Phase Transition of a Crystalline Solid Europium Germanate NaEuGeO4 | |
| Nagarajan et al. | Antimony substitution leading to structural transformation (Bixbyite→ Fluorite) and altering the optical band gap in Y2O3 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181102 |