CN109504373A - A kind of chlorine nitrogen codope carbon quantum dot and its preparation method and application based on the preparation of discarded pomelo peel - Google Patents
A kind of chlorine nitrogen codope carbon quantum dot and its preparation method and application based on the preparation of discarded pomelo peel Download PDFInfo
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- CN109504373A CN109504373A CN201811446248.5A CN201811446248A CN109504373A CN 109504373 A CN109504373 A CN 109504373A CN 201811446248 A CN201811446248 A CN 201811446248A CN 109504373 A CN109504373 A CN 109504373A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- 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"
- G01N2021/6432—Quenching
Abstract
The invention belongs to Illuminant nanometer field of material technology, a kind of chlorine nitrogen codope carbon quantum dot and its preparation method and application based on the preparation of discarded pomelo peel is provided, the preparation method simple process, raw material sources are extensive and cheap, preparation condition requires low and environmental-friendly, it is easy to spread in common laboratory energy rapid synthesis.Blue-fluorescence chlorine nitrogen codope carbon quantum dot prepared by the present invention, the carbon quantum dot can 2,4,6- trinitrophenols (PA) in Sensitive Detection water environment.Using discarded pomelo peel as carbon source, concentrated hydrochloric acid is acidulant and dopant, is made by concentrated acid acidization.Using discarded pomelo peel as raw material, preparation process is simple, and it requires low, prepared chlorine nitrogen codope carbon quantum dot fluorescence quantum efficiency is higher, has good water-soluble and dispersibility, excellent ion and light durability, to 2 in water body, 4,6- trinitrophenols (PA) have excellent selectivity, can be used for the detection of PA in water body.
Description
Technical field
The invention belongs to Illuminant nanometer field of material technology more particularly to fluorescent carbon quantum dots, and in particular to one kind is based on
The chlorine nitrogen codope carbon quantum dot and its preparation method and application of discarded pomelo peel preparation.
Background technique
Fluorescent carbon quantum dot is a kind of zero dimension torispherical nano particle of the partial size less than 10 nm, mainly by tri- kinds of members of C, H, O
Element composition, it is easy to be surface modified and functionalization, there is excellent light resistance, hypotoxicity, good water solubility is adjustable
Luminescence generated by light (PL) performance, brilliant multiphoton excitation (conversion) performance, electrochemical luminescence performance.
Picric acid (PA also known as 2,4,6- trinitrophenols) is a kind of aromatic nitro compound of danger.Due to its explosion
Property high (be higher than 2,4,6-trinitrotoluene, i.e. TNT), therefore be widely used as the original of military explosive, rocket fuel and fireworks
Material, while being widely used in biomedical laboratory and leather, pharmacy and dye industry as a kind of common reagent again.PA
Containing phenolic hydroxyl group and nitro, it is highly soluble in water, but biological degradability is poor.Therefore, being widely used for PA will cause drinking water or ground
Table water pollution, causes human health system to come to harm, such as stimulation skin, anaemia, dysfunction of liver etc., while can also be to exhaling
Haustorium official causes serious harm.Currently, PA is considered as a kind of environmental contaminants, there is serious three-induced effect.Therefore, to water
PA, which carries out real-time monitoring, in body has potential meaning and application value.
Summary of the invention
The purpose of the present invention is to provide a kind of chlorine nitrogen codope carbon quantum dots and its system based on the preparation of discarded pomelo peel
Preparation Method and application, the preparation method simple process, raw material sources are extensively and price is just declared, and preparation condition requires low and environment friendly
It is good, it is easy to spread in common laboratory energy rapid synthesis.Blue-fluorescence chlorine nitrogen codope carbon quantum prepared by the present invention
Point, the carbon quantum dot can 2,4,6- trinitrophenols (PA) in Sensitive Detection water environment.
The present invention is realized by following technical solution:
A kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel, the chlorine nitrogen codope carbon quantum dot is to discard shaddock
Skin is carbon source, and concentrated hydrochloric acid is acidulant and dopant, is made by concentrated acid acidization.
Specific step is as follows for the preparation method of the chlorine nitrogen codope carbon quantum dot:
(1) discarded pomelo peel is chosen, all moisture of removal is dried in 50 DEG C of baking ovens after removing white flesh chopping, obtains dry shaddock
Skin, pulverizer crush to obtain pomelo peel powder；
(2) 0.5-6g pomelo peel powder is taken, the mixed solution of secondary water and concentrated hydrochloric acid that volume ratio is 1:9-9:1, ultrasound is added
It after 10 min, is placed on heated at constant temperature blender, in oil bath heated at constant temperature 30-180 min, obtains dark thick solution；
(3) after solution is cooled to room temperature, centrifugation and filtering removal insoluble matter obtain yellow solution；With 500-1000 Da's
Bag filter is handled 3 days, obtains pure chlorine nitrogen codope carbon quantum dot aqueous solution, chlorine nitrogen codope carbon amounts is obtained after freeze-drying
Son point powder.
Baking oven dries 1.8-2.3h in step (1).
Concentrated hydrochloric acid concentration in step (2) is 38%, and the total volume of the mixed solution of secondary water and concentrated hydrochloric acid is 4-50 mL；
Ultrasound condition are as follows: 10-30 min；Heating temperature is 50-90 DEG C.
Centrifugal condition in step (3) are as follows: 8000-10000 rpm/min, centrifugation time are as follows: 8-15 min.
A kind of application of the chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel, the chlorine nitrogen codope carbon quantum
Point detects 2,4,6- trinitrophenol, that is, picric acid PA application as fluorescence probe in water body.
2,4,6- trinitrophenol, that is, picric acid PA is detected in water body method particularly includes:
(1) prepare fluorescence probe stock solution: 0.1g chlorine nitrogen codope carbon quantum dot powder is dissolved in 10 mL secondary waters, is formulated as
The chlorine nitrogen codope carbon quantum dot stock solution of 10 mg/mL；
(2) fluorescence emission spectrum of chlorine nitrogen codope carbon quantum dot is measured: by 50 μ L carbon quantum dot stock solutions and 2 mL secondary waters
It is uniformly mixed, is added in fluorescence cuvette, the PA solution of 0.01 mol/L is gradually added dropwise into fluorescence cuvette, drip every time
Add 0.2 μ L, after 2 min are added dropwise, the fluorescence emission spectrum of chlorine nitrogen codope carbon quantum dot is measured, in 0.95-90 μm of ol/L model
In enclosing, linear relationship, linear equation F is presented in the concentration of PA and the fluorescence intensity of chlorine nitrogen codope carbon quantum dot0/F =
0.01902 [PA]+0.9456, relative coefficient R2 = 0.9965；
(3) water body detection to be measured: 50 μ L chlorine nitrogen codope carbon quantum dot stock solutions are uniformly mixed with 2 mL water sample to be measured, are added
Enter into fluorescence cuvette, measures fluorescence spectrum；The PA solution of 0.01 mol/L is added into fluorescence cuvette, is added dropwise every time
0.2 μ L measures fluorescence spectrum again, calculates relative standard deviation RSD and mark-on reclaims in water sample to be measured after 2 min are added dropwise
Rate.
The chlorine nitrogen codope carbon quantum dot is 0.95~90 μm of ol/L to the range of linearity that PA in water body is detected, minimum
Detection is limited to 0.60 μm of ol/L.
The fluorescence quantum yield of the chlorine nitrogen codope carbon quantum dot is between 2.18%-17.59%.
It is double-doped that using discarded pomelo peel as raw material, by green easy concentrated acid acidization chlorine nitrogen can be quickly made in the present invention
Miscellaneous carbon quantum dot, raw material is cheap and easy to get, and synthetic method is simple and efficient, and reaction condition is mild and environmental-friendly, in common laboratory
It can be rapidly completed, it is easy to spread.Prepared carbon quantum dot can be used for the detection of PA in environmental water sample as fluorescence probe.
Detailed description of the invention
Fig. 1 is the ultra-violet absorption spectrum and fluorescence emission spectrum of chlorine nitrogen codope carbon quantum dot prepared by embodiment 1；
Fig. 2 is the XPS spectrum figure of chlorine nitrogen codope carbon quantum dot prepared by embodiment 1,2(a) be the total spectrogram of XPS, 2(b) it is C1s
Open score figure, 2(c) be Cl2p open score figure, 2(d) it is N1s open score figure；
Fig. 3 is the infrared spectrogram of chlorine nitrogen codope carbon quantum dot prepared by embodiment 1, and abscissa is Detection wavelength in figure, is indulged
Coordinate is transmitance；
Fig. 4 is fluorescence spectra of the chlorine nitrogen codope carbon quantum dot of the preparation of embodiment 1 under xenon lamp irradiation；
Fig. 5 is fluorescence spectra of the chlorine nitrogen codope carbon quantum dot of the preparation of embodiment 1 in the solion of various concentration；
Fig. 6 is fluorescence spectra of the chlorine nitrogen codope carbon quantum dot of the preparation of embodiment 1 in different pH solution；
Fig. 7 is fluorescence of the chlorine nitrogen codope carbon quantum dot of the preparation of embodiment 1 in different metal ions and PA analog solution
Strength Changes figure；
Fig. 8 be embodiment 1 prepare chlorine nitrogen codope carbon quantum dot in be gradually added into PA after, chlorine nitrogen codope carbon quantum dot it is glimmering
Light spectrogram；
Fig. 9 is the linear relationship between the fluorescence and PA concentration of chlorine nitrogen codope carbon quantum dot prepared by embodiment 1.
Specific embodiment
With reference to the accompanying drawing and specific embodiment makes further explanation to the present invention, and embodiment gives detailed reality
Mode and specific operating process are applied, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1: a kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel, the chlorine nitrogen codope carbon quantum
For point using discarded pomelo peel as carbon source, concentrated hydrochloric acid is acidulant and dopant, is made by concentrated acid acidization.
Specific step is as follows for the preparation method of the chlorine nitrogen codope carbon quantum dot:
(1) discarded pomelo peel is chosen, all moisture of 2h removal is dried in 50 DEG C of baking ovens after removing white flesh chopping, obtains dry shaddock
Skin, pulverizer crush to obtain pomelo peel powder；
(2) 2 g pomelo peel powder are weighed in beaker, the mixed solution of 10 mL secondary waters and 5 mL concentrated hydrochloric acids, ultrasound 10 is added
Min obtains homogeneous solution.
(3) beaker equipped with mixed solution is placed in constant temperature blender with magnetic force, the heated at constant temperature 60 in 90 DEG C of oil baths
Min obtains dark thick solution.
(4) after solution is cooled to room temperature, by being centrifuged and filtering, insoluble matter is removed, yellow solution is obtained.
(5) it is handled 3 days using the bag filter of 500-1000 Da, obtains pure chlorine nitrogen codope carbon quantum dot aqueous solution.
Chlorine nitrogen codope carbon quantum dot solid powder will be obtained after the freeze-drying of above-mentioned chlorine nitrogen codope carbon quantum dot aqueous solution
End, the relative fluorescence quantum yield (using quinine sulfate as standard) of prepared chlorine nitrogen codope carbon quantum dot are 17.59%.
Obtained chlorine nitrogen codope carbon quantum dot is characterized, the result is shown in Figure 1-6.
Fig. 1 is the ultra-violet absorption spectrum and fluorescence emission spectrum of chlorine nitrogen codope carbon quantum dot；It can from fluorogram
Out, excitation wavelength is 325 nm, and maximum emission wavelength is 460 nm, from uv-spectrogram as can be seen that in 278 nm and 328 nm
The characteristic absorption peak at place respectively corresponds n → π * transition of C=O and nitrogen chlorine adulterates caused surface defect.
Fig. 2 is the XPS spectrum figure of chlorine nitrogen codope carbon quantum dot, 3(a) be the total spectrogram of XPS, 3(b) be C1s open score figure, 3
(c) it is Cl2p open score figure, 3(d) it is N1s open score figure.It can be seen from the figure that successfully adulterating N in chlorine nitrogen codope carbon quantum dot
With Cl element, and on chlorine nitrogen codope carbon quantum dot surface and internal a large amount of C-N, the functional groups such as C=O, C-Cl are formed.
Fig. 3 is the infrared spectrogram of chlorine nitrogen codope carbon quantum dot, and abscissa is Detection wavelength in figure, and ordinate is to penetrate
Rate.As seen from the figure, 3403 cm-1With 2924 cm-1The stretching vibration absworption peak of respectively O-H and C-H, 1417 cm-1With
1230 cm-1The stretching vibration absworption peak of respectively O-C=O and C-O-C, 1734 cm-1For the bending vibration absorption peak of CON-H,
819 cm-1For the stretching vibration absworption peak of C-Cl.
Fig. 4 is fluorescence spectra of the chlorine nitrogen codope carbon quantum dot under xenon lamp irradiation.As seen from the figure, it is persistently shone under xenon lamp
After 180 min of raCl nitrogen codope carbon quantum dot, there is no significant changes for the fluorescence intensity of chlorine nitrogen codope carbon quantum dot, say
Bright chlorine nitrogen codope carbon quantum dot has good fast light Bleachability.
Fig. 5 is fluorescence spectra of the chlorine nitrogen codope carbon quantum dot in the solion (KCl) of various concentration.It can by figure
Know, as ion concentration increases significant change does not occur for the fluorescence intensity of chlorine nitrogen codope carbon quantum dot, illustrates chlorine nitrogen codope
Carbon quantum dot has good ion stability.
Fig. 6 is fluorescence spectra of the chlorine nitrogen codope carbon quantum dot in different pH solution.As seen from the figure, chlorine nitrogen codope
Carbon quantum dot is able to maintain higher fluorescence intensity within the scope of near-neutral pH, shows chlorine nitrogen codope carbon quantum dot different pH's
There is potential application value in actual water sample detection.
Fig. 7 is the influence diagram of different metal ions and PA analog solution to chlorine nitrogen codope carbon quantum dot fluorescence, by scheming
It is found that only PA can be such that the fluorescence of chlorine nitrogen codope carbon quantum dot quenches, F/F0Significant changes occur, illustrate that chlorine nitrogen is double-doped
Miscellaneous carbon quantum dot has good selectivity to PA.
Embodiment 2: a kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel, the chlorine nitrogen codope carbon quantum
For point using discarded pomelo peel as carbon source, concentrated hydrochloric acid is acidulant and dopant, is made by concentrated acid acidization.
Specific step is as follows for the preparation method of the chlorine nitrogen codope carbon quantum dot:
(1) discarded pomelo peel is chosen, all moisture of removal is dried in 50 DEG C of baking ovens after removing white flesh chopping, obtains dry shaddock
Skin, pulverizer crush to obtain pomelo peel powder；
(2) 1 g pomelo peel powder is weighed in beaker, and the mixed solution of 7 mL secondary waters and 8 mL concentrated hydrochloric acids, ultrasound 10 is added
Min obtains homogeneous solution.
(3) beaker equipped with mixed solution is placed in constant temperature blender with magnetic force, the heated at constant temperature 80 in 80 DEG C of oil baths
Min obtains dark thick solution.
(4) after solution is cooled to room temperature, by being centrifuged and filtering, insoluble matter is removed, yellow solution is obtained.
(5) it is handled 3 days using the bag filter of 500-1000 Da, obtains pure chlorine nitrogen codope carbon quantum dot aqueous solution.
Chlorine nitrogen codope carbon quantum dot solid powder will be obtained after the freeze-drying of above-mentioned chlorine nitrogen codope carbon quantum dot aqueous solution
End, the relative fluorescence quantum yield (using quinine sulfate as standard) of prepared chlorine nitrogen codope carbon quantum dot are 13.75%.
Embodiment 3: a kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel, the chlorine nitrogen codope carbon quantum
For point using discarded pomelo peel as carbon source, concentrated hydrochloric acid is acidulant and dopant, is made by concentrated acid acidization.
Specific step is as follows for the preparation method of the chlorine nitrogen codope carbon quantum dot:
(1) 4 g pomelo peel powder are weighed in beaker, the mixed solution of 5 mL secondary waters and 10 mL concentrated hydrochloric acids, ultrasound 10 is added
Min obtains homogeneous solution.
(2) beaker equipped with mixed solution is placed in constant temperature blender with magnetic force, the heated at constant temperature 120 in 90 DEG C of oil baths
Min obtains dark thick solution.
(3) after solution is cooled to room temperature, by being centrifuged and filtering, insoluble matter is removed, yellow solution is obtained.
(4) it is handled 3 days using the bag filter of 500-1000 Da, obtains pure chlorine nitrogen codope carbon quantum dot aqueous solution.
Chlorine nitrogen codope carbon quantum dot solid powder will be obtained after the freeze-drying of above-mentioned chlorine nitrogen codope carbon quantum dot aqueous solution
End, the relative fluorescence quantum yield (using quinine sulfate as standard) of prepared chlorine nitrogen codope carbon quantum dot are 12.98%.
Embodiment 4: a kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel, the chlorine nitrogen codope carbon quantum
For point using discarded pomelo peel as carbon source, concentrated hydrochloric acid is acidulant and dopant, is made by concentrated acid acidization.
Specific step is as follows for the preparation method of the chlorine nitrogen codope carbon quantum dot:
Step 1,6 g pomelo peel powder are weighed in beaker, the mixed solution of 2 mL secondary waters and 13 mL concentrated hydrochloric acids is added, are surpassed
10 min of sound obtains homogeneous solution.
Step 2, the beaker equipped with mixed solution is placed in constant temperature blender with magnetic force, the heated at constant temperature in 90 DEG C of oil baths
180 min obtain dark thick solution.
Step 3, after solution is cooled to room temperature, by being centrifuged and filtering, insoluble matter is removed, yellow solution is obtained.
Step 4, it is handled 3 days using the bag filter of 500-1000 Da, it is water-soluble to obtain pure chlorine nitrogen codope carbon quantum dot
Liquid.
Chlorine nitrogen codope carbon quantum dot solid powder will be obtained after the freeze-drying of above-mentioned chlorine nitrogen codope carbon quantum dot aqueous solution
End, the relative fluorescence quantum yield (using quinine sulfate as standard) of prepared chlorine nitrogen codope carbon quantum dot are 6.68%.
Embodiment 5: a kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel, the chlorine nitrogen codope carbon quantum
For point using discarded pomelo peel as carbon source, concentrated hydrochloric acid is acidulant and dopant, is made by concentrated acid acidization.
Specific step is as follows for the preparation method of the chlorine nitrogen codope carbon quantum dot:
Step 1,0.5 g pomelo peel powder is weighed in beaker, and the mixed solution of 13 mL secondary waters and 2 mL concentrated hydrochloric acids is added,
10 min of ultrasound obtain homogeneous solution.
Step 2, the beaker equipped with mixed solution is placed in constant temperature blender with magnetic force, the heated at constant temperature 30 in 50 DEG C of oil baths
Min obtains dark thick solution.
Step 3, after solution is cooled to room temperature, by being centrifuged and filtering, insoluble matter is removed, yellow solution is obtained.
Step 4, it is handled 3 days using the bag filter of 500-1000 Da, it is water-soluble to obtain pure chlorine nitrogen codope carbon quantum dot
Liquid.
Chlorine nitrogen codope carbon quantum dot solid powder will be obtained after the freeze-drying of above-mentioned chlorine nitrogen codope carbon quantum dot aqueous solution
End, the relative fluorescence quantum yield (using quinine sulfate as standard) of prepared chlorine nitrogen codope carbon quantum dot are 2.28%.
Embodiment 6: 0.1 g of chlorine nitrogen codope carbon quantum dot powder of the preparation of embodiment 1 is weighed, 10 mL secondary waters are dissolved in
In, it is formulated as the chlorine nitrogen codope carbon quantum dot stock solution of 10 mg/mL.By 50 μ L carbon quantum dot stock solutions and 2 mL secondary waters
It is uniformly mixed, is added in fluorescence cuvette, measure the fluorescence emission spectrum of chlorine nitrogen codope carbon quantum dot, record its best hair
Maximum intensity F under ejected wave is long0, backward fluorescence cuvette in be added dropwise 50 μ L(0.01 mol/L of PA solution), measure its fluorescence
Emission spectrum records its maximum intensity F, hereafter, PA solution is substituted for other interference solution (Al3+, Cu2+, Mg2+, Cd2+, Cr3 +, K+, Pb2+, Co2+, Fe3+, Zn2+, Mn2+, Na+, Fe2+, Ba2+, Ca2+, Ag+, Ni2+, 2-NT, CH3NO3, phenol, DNT) and in repetition
Step is stated to be measured and record.To glimmering before and after the chlorine nitrogen codope carbon quantum dot that different ions solution and phenols solution is added dropwise
Light changes F/F0It is compared, as a result sees Fig. 8.As seen from the figure, with the addition of PA, the fluorescence of chlorine nitrogen codope carbon quantum dot by
It is decrescence weak, show that chlorine nitrogen codope carbon quantum dot has good response relation to PA, there is high selectivity and strong sensitivity.
Embodiment 7: 0.1 g of chlorine nitrogen codope carbon quantum dot powder of the preparation of embodiment 1 is weighed, 10 mL secondary waters are dissolved in
In, it is formulated as the chlorine nitrogen codope carbon quantum dot stock solution of 10 mg/mL.By 50 μ L carbon quantum dot stock solutions and 2 mL secondary waters
It is uniformly mixed, is added in fluorescence cuvette, PA solution (0.01 mol/L) is gradually added dropwise into fluorescence cuvette, be added dropwise every time
0.2 μ L after 2 min are added dropwise, measure the fluorescence emission spectrum of chlorine nitrogen codope carbon quantum dot, as a result sees Fig. 8.In 0.95-90 μ
Within the scope of mol/L, linear relationship is presented in the concentration of PA and the fluorescence intensity of chlorine nitrogen codope carbon quantum dot, as a result sees Fig. 9, linearly
Equation is F0/ F=0.01902 [PA]+0.9456, relative coefficient R2 =0.9965, minimum detectability is 0.60 μm of ol/
L.As shown in Figure 9, when PA concentration is 0.95-90 μm of ol/L, PA concentration is in chlorine nitrogen codope carbon quantum dot change in fluorescence amount
Existing good linear relationship illustrates that chlorine nitrogen codope carbon quantum dot is expected to be used for PA detection.
Embodiment 8: 50 μ L chlorine nitrogen codope carbon quantum dot stock solutions are mixed with 2 mL tap water or Wutai Mountain water sample
It is even, it is added in fluorescence cuvette, measures fluorescence spectrum；A certain amount of PA solution (0.01 is added into fluorescence cuvette
Mol/L), fluorescence spectrum is measured again, is calculated relative standard deviation (RSD) and recovery of standard addition in four kinds of water samples, is as a result seen
Table 1.As seen from table, originally the recovery of standard addition of PA is between 95.86-105.16% in water sample and three kinds of Wutai Mountain water samples, phase
To standard deviation (RSD) less than 7.97%, illustrate chlorine nitrogen codope carbon quantum dot in water body detection PA there are good effect,
It is expected to be prepared as a kind of good fluorescence probe of water body detection PA concentration.
Table 1: the experimental result of chlorine nitrogen codope carbon quantum dot prepared by embodiment 1 for PA detection in actual sample
Claims (8)
1. a kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel, it is characterised in that: the chlorine nitrogen codope carbon amounts
For son point using discarded pomelo peel as carbon source, concentrated hydrochloric acid is acidulant and dopant, is made by concentrated acid acidization.
2. a kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel according to claim 1, feature exist
In: specific step is as follows for the preparation method of the chlorine nitrogen codope carbon quantum dot:
(1) discarded pomelo peel is chosen, all moisture of removal is dried in 50 DEG C of baking ovens after removing white flesh chopping, obtains dry shaddock
Skin, pulverizer crush to obtain pomelo peel powder；
(2) 0.5-6g pomelo peel powder is taken, the mixed solution of secondary water and concentrated hydrochloric acid that volume ratio is 1:9-9:1, ultrasound is added
It after 10 min, is placed on heated at constant temperature blender, in oil bath heated at constant temperature 30-180 min, obtains dark thick solution；
(3) after solution is cooled to room temperature, centrifugation and filtering removal insoluble matter obtain yellow solution；With 500-1000 Da's
Bag filter is handled 3 days, obtains pure chlorine nitrogen codope carbon quantum dot aqueous solution, chlorine nitrogen codope carbon amounts is obtained after freeze-drying
Son point powder.
3. a kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel according to claim 2, feature exist
In: baking oven dries 1.8-2.3h in step (1).
4. a kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel according to claim 2, feature exist
In: the concentrated hydrochloric acid concentration in step (2) is 38%, and the total volume of the mixed solution of secondary water and concentrated hydrochloric acid is 4-50 mL；Ultrasound
Condition are as follows: 10-30 min；Heating temperature is 50-90 DEG C.
5. a kind of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel according to claim 2, feature exist
In: centrifugal speed in step (3) are as follows: 8000-10000 rpm/min；Centrifugation time is 8-15 min.
6. a kind of application of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel as claimed in claim 1 or 2,
Be characterized in that: the chlorine nitrogen codope carbon quantum dot detects 2,4,6- trinitrophenol i.e. bitter taste as fluorescence probe in water body
The application of sour PA.
7. a kind of application of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel according to claim 6,
It is characterized in that: detecting the i.e. picric acid PA's of 2,4,6- trinitrophenol in water body method particularly includes:
(1) prepare fluorescence probe stock solution: 0.1g chlorine nitrogen codope carbon quantum dot powder is dissolved in 10 mL secondary waters, is formulated as
The chlorine nitrogen codope carbon quantum dot stock solution of 10 mg/mL；
(2) fluorescence emission spectrum of chlorine nitrogen codope carbon quantum dot is measured: by 50 μ L carbon quantum dot stock solutions and 2 mL secondary waters
It is uniformly mixed, is added in fluorescence cuvette, the PA solution of 0.01 mol/L is gradually added dropwise into fluorescence cuvette, drip every time
Add 0.2 μ L, after 2 min are added dropwise, the fluorescence emission spectrum of chlorine nitrogen codope carbon quantum dot is measured, in 0.95-90 μm of ol/L model
In enclosing, linear relationship, linear equation F is presented in the concentration of PA and the fluorescence intensity of chlorine nitrogen codope carbon quantum dot0/F =
0.01902 [PA]+0.9456, relative coefficient R2 = 0.9965；
(3) water body detection to be measured: 50 μ L chlorine nitrogen codope carbon quantum dot stock solutions are uniformly mixed with 2 mL water sample to be measured, are added
Enter into fluorescence cuvette, measures fluorescence spectrum；The PA solution of 0.01 mol/L is added into fluorescence cuvette, is added dropwise every time
0.2 μ L measures fluorescence spectrum after 2 min are added dropwise again, and the relative standard deviation RSDs and mark-on calculated in water sample to be measured is returned
Yield.
8. a kind of application of chlorine nitrogen codope carbon quantum dot based on the preparation of discarded pomelo peel according to claim 6,
Be characterized in that: the chlorine nitrogen codope carbon quantum dot is 0.95~90 μm of ol/L to the range of linearity that PA in water body is detected, minimum
Detection is limited to 0.60 μm of ol/L.
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