CN106744808A - A kind of carbon quantum dot with fish scale as raw material and its preparation method and application - Google Patents
A kind of carbon quantum dot with fish scale as raw material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of carbon quantum dot with fish scale as raw material and its preparation method and application.After fish scale is mixed with ultra-pure water, it is transferred in reactor, is put into rupture pressure disc, seal, be placed in microwave attenuation materials instrument, heating using microwave obtains suspension；Suspension is stood, room temperature is cooled to, filtrate is filtered to take, concentrate is obtained；Concentrate two ends dialysis clamp is clipped in dialysis bag, under conditions of 4 DEG C of darknesses, dialysed 24h, and a ultra-pure water is changed per 8h, obtains carbon quantum dot.The inventive method is simply novel, reclaims discarded fish scale, and natural non-impurity-doped, quantum yield is high, turns waste into wealth, and develops a circular economy, effective refuse reclamation and resource.And the present invention is conducive to the quick detection of mercury ion, can discover problems and solve them early, the emergency preplan of Erecting and improving, preventing and treating further pollution.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, it is specifically a kind of with the fish scale rich in natural cystein be carbon
Source, Water-soluble carbon quantum dot, and the application during quick detection mercury ion are prepared using microwave attenuation materials method.
Background technology
Mercury be it is a kind of can long-term existence in environment, and with persistence, easy animal migration, bioconcentration high and height are biological
The material of the characteristics such as toxicity.Mercury and its derivative organic mercury, can be in air as the important poisonous and harmful environmental contaminants of a class
Exist for a long time with food chain, and can migrate at a distance.China is with a long history using mercury, also once occurs because of industry in history
The accident of mercury pollution caused with mercury, current some mercury ores and non-ferrous metal metallurgy area water body in the neighbourhood, soil and rice
In still can detect the mercury of higher concentration, mercury pollution and control have become the focus of Present Global concern, difficult point and focus and ask
Topic, the Environmental risk management of mercury pollution has been in the world trend of the times.Mercury is main with Elemental Mercury in nature, inorganic
3 kinds of forms of mercury and organic mercury are present, by biological enrichment, in entering food chain, and the excessive Hg of absorption of human body2+After can lead
The infringement of central nervous system, liver, kidney and enteron aisle is caused, even death can be caused when serious.Therefore, Hg in organism and environment2+
Detection it is particularly significant.In recent years, Hg is detected2+Method mainly have Atomic absorption-emission spectrometry, AAS, efficiently
Liquid chromatography, electrochemical process and XRF etc..
XRF is single-minded because with convenient, receives much concern the advantages of sensitive and in good time in situ detection.It is several recently
Year, the research of quantum dot is very active, and quantum dot is usually from lead, to be extracted in the mixture of cadmium and silicon, but this tittle
Son point is general poisonous, also there is very big harm to environment.The scientist of Clemson University of the U.S. produces a kind of new first
Carbon nanomaterial-carbon quantum dot, similar with various metal quantum points, carbon quantum dot can send bright in the case of illumination
Light.Carbon nano-particles have very big surface area, and this nano-particle compares macroscopical carbon, with very peculiar physics and change
Property is learned, for opposing metallic quantum dot, carbon quantum dot nonhazardous effect, to the harm very little of environment, preparation cost is cheap, is
A kind of environmentally friendly fluorescent nano material compared to semiconductor-quantum-point with similar optical performance.Carbon quantum dot is removed and possesses light
Function admirable is learned, outside the advantage that conventional semiconductors quantum dot possesses such as size is small, it also has cytotoxicity low, bio-compatible
Property it is good, it is easy to extensive synthesis and functional modification, the unrivaled advantage such as preparation cost is cheap and reaction condition is gentle.It
Including improving biology sensor, have in the very wide field of medical imaging devices and small light emitting diode using preceding
Scape.
At present, in detection Hg2+Carbon quantum dot prepare, in order to improve the fluorescence intensity of carbon quantum dot and to Hg2+Spy
Different selectivity, often adulterated nitrogen, element sulphur, and the metallic element such as other Au, Cd, and this mode can be improved to a certain extent
Quantum yield, strengthens to Hg2+Single-minded recognition detection ability, but often artificial doping can all influence quantum dot self character, change
Composition, can influence absorbing ability, change its electronic structure, can reduce quantum dot itself luminous power.
The content of the invention
Environment is polluted in order to solve mercury ion, detects the problem of mercury ion on the spot in time, present invention design is a kind of
The carbon quantum dot and the new method of quick detection mercury ion prepared as raw material with fish scale.
The technical solution adopted by the present invention is：A kind of carbon quantum dot with fish scale as raw material, preparation method is as follows：
(1) fish scale is cleaned, is dried, shredded；The preferred grass carp scales of described fish scale；
(2) after fish scale is mixed with ultra-pure water, it is transferred in reactor, is put into rupture pressure disc, seal, places into Microwave Water
In thermal synthesis instrument, heating using microwave obtains suspension；
(3) suspension is stood, is cooled to room temperature, filter to take filtrate, obtain concentrate；
(4) concentrate two ends dialysis clamp is clipped in dialysis bag, under conditions of 4 DEG C of darknesses, dialyse 24h, is changed per 8h
Ultra-pure water, obtains carbon quantum dot.
A kind of above-mentioned carbon quantum dot with fish scale as raw material, fish scale is 1g with the solid-to-liquid ratio of ultra-pure water:70-90mL.
A kind of above-mentioned carbon quantum dot with fish scale as raw material, in microwave attenuation materials instrument, seven ranks of heating using microwave point
Section：First stage is warming up to 120 DEG C in 10min；Second stage is in 120 DEG C of constant temperature 5min；Phase III is warming up in 10min
150℃；Fourth stage is in 150 DEG C of constant temperature 5min；5th stage was warming up to 180 DEG C in 10min；6th stage is in 180 DEG C of constant temperature
5min；7th stage was the stage of reaction, and reaction temperature is 210 DEG C, heats 2h；Microwave attenuation materials instrument parameter is set, and power is
1000W, upper pressure limit is 1.500MPa.
A kind of above-mentioned carbon quantum dot with fish scale as raw material, the molecular weight of dialysis bag is 3500Da.
Application of the above-mentioned carbon quantum dot with fish scale as raw material in specific detection mercury ion.Method is as follows：Normal
Under the conditions of normal temperature and pressure, by mercury solution to be measured and carbon quantum dot solution 1:1 mixing, with ultra violet lamp, whether observation fluorescence is quenched.
The present invention, using microwave attenuation materials instrument, using the natural fish scale rich in cysteine as carbon source, prepares water
Dissolubility carbon quantum dot.It is well known that the synthetic method of carbon quantum dot has various, 2 classes are generally can be divided into：From top to bottom synthetic method and
Synthetic method from bottom to top, the former is based on itself larger carbon skeleton (such as carbon target) from the synthesis side of nano carbon particle under upper peeling
Method, the latter is then directly to be modified with smaller carbon particle, passivation, so that the method for synthesizing fluorescent carbon quantum dot.From top to bottom
Synthetic method, it is difficult to which carbon skeleton is thoroughly ground into nano particle, yield is extremely low；From bottom to top in synthetic method, if having with macromolecular
Machine thing is raw material, and macromolecular is become small molecule, a large amount of non-carbon are eliminated in carbonisation by the mode generally by carbonization
Material, therefore yield is also very low (highest only up to 1%).The general unstressed configuration of carbon quantum dot or fluorescence quantum yield for just preparing are relatively low
(major part be no greater than 10%), it is impossible to meet application, be such as used for fluorescence labeling or bio-imaging condition.Then pass through at modification
Manage to stablize its optical property and improve fluorescence quantum yield.Modifying principle is：Being introduced on carbon quantum dot surface includes that amino exists
Some interior special groups, fill up the defect on carbon quantum dot surface or carbon quantum dot surface is produced energy potential well, send out fluorescence
Penetrate more stable, so as to improve fluorescence quantum yield.The present invention utilizes this synthetic method from bottom to top of microwave hydrothermal, with rich in cysteine
Natural fish scale as prepare carbon quantum dot carbon source, under conditions of unmodified, quantum yield is that can reach 20%, not only
Effectively improve synthetic yield and the reaction time is greatly shortened.
The beneficial effects of the invention are as follows：
1. the invention discloses a kind of new side for preparing carbon quantum dot and quick detection mercury ion as raw material with grass carp scales
Method.Containing abundant crude protein and ash content in grass carp scales, also a small amount of fat and sugar class material is wherein rich in thick protein
Substantial amounts of cysteine, contains sulfydryl in cysteine.Using this characteristic of sulphur parent's mercury, using grass carp scales as carbon source, utilize
The method of microwave attenuation materials, prepares carbon quantum dot, to Hg2+Carry out specific detection.
2. the present invention is stable in properties using carbon quantum dot prepared by microwave-hydrothermal method, and the reaction time is short, simple to operate, is easy to get
To Water-soluble carbon quantum dot, and fluorescence intensity is strong, and quantum yield is high, and heat endurance is good, and anti-light bleaching power is strong, to Hg2+'s
Detection has selection specificity, other ions coexisted with mercury in water body, and same cycle, same to main group, has phase with mercury ion
Like the metal ion of chemical property, the fluorescence intensity to the carbon quantum dot is not disturbed significantly.
3. the present invention, carbon quantum dot is obtained by the use of natural fish scale as raw material, without other elements doping and modification, does not have by-product
Thing, neither changes the fluorescence activity of itself, and can efficient quick detection Hg2+, safety and environmental protection is pollution-free, can be applied to prepare glimmering
Light probe and biology sensor etc., are a kind of sensitive materials that preferably can be applied to prepare high sensitivity thin-film type senser element
Material.
4. the inventive method is simply novel, reclaims discarded grass carp scales, and natural non-impurity-doped, quantum yield is high, turns waste into wealth,
Develop a circular economy, effective refuse reclamation and resource.And the present invention is conducive to the quick detection of mercury ion, Neng Gouji
Early discover problems and solve them, the emergency preplan of Erecting and improving, preventing and treating further pollution
Brief description of the drawings
Fig. 1 is Water-soluble carbon quantum dot uv absorption spectra prepared by embodiment 1.
Fig. 2 a are Water-soluble carbon quantum dot fluorescence emission spectrogram of compound (320-355nm) prepared by embodiment 1.
Fig. 2 b are Water-soluble carbon quantum dot fluorescence emission spectrogram of compound (355-400nm) prepared by embodiment 1.
Fig. 3 is Fourier's infrared spectrum of Water-soluble carbon quantum dot prepared by embodiment 1.
Fig. 4 is the X-ray powder diffraction figure of Water-soluble carbon quantum dot prepared by embodiment 1.
Fig. 5 be embodiment 1 prepare Water-soluble carbon quantum dot in the presence of other metal ions to fluorescence intensity interference figure.
Fig. 6 is that Water-soluble carbon quantum dot prepared by embodiment 1 is quenched intensity contrast figure under condition of different pH to mercury ion.
Fig. 7 be embodiment 1 prepare Water-soluble carbon quantum dot in the presence of various concentrations mercury ion fluorescence intensity influence figure.
Specific embodiment
A kind of carbon quantum dot with grass carp scales as raw material of embodiment 1
(1) preparation method is as follows
1) grass carp scales are reclaimed, is rinsed repeatedly with warm water, remove unnecessary blood and grease, stainless steel is laid in after cleaning
Ventilation is dried on disk, is shredded.
2) by solid-to-liquid ratio 1g:80mL, after 0.5g grass carp scales are mixed with 40mL ultra-pure waters, is transferred in reactor, puts
Enter in rupture pressure disc, sealing is then placed in microwave attenuation materials instrument, the heating using microwave 2.00h at 210 DEG C, obtain brown color and hang
Turbid liquid.
In microwave attenuation materials instrument, microwave heating process is：In microwave attenuation materials instrument, seven ranks of heating using microwave point
Section：First stage is warming up to 120 DEG C in 10min；Second stage is in 120 DEG C of constant temperature 5min；Phase III is warming up in 10min
150℃；Fourth stage is in 150 DEG C of constant temperature 5min；5th stage was warming up to 180 DEG C in 10min；6th stage is in 180 DEG C of constant temperature
5min；7th stage, to be warming up to 210 DEG C, heated 2h；Microwave attenuation materials instrument parameter is set, and power is 1000W, upper pressure limit
It is 1.500MPa.
3) brown color suspension is put into fume hood and stands, room temperature is cooled to, first with 15-20 μm of filtered on buchner funnel
Remove unreacted bulk fish scale, take filtrate.Centrifuge is used again, after elder generation is with 1500rpm low-speed centrifugals, then with 3500rpm at a high speed
Centrifugation, is centrifuged 10min, obtains yellow transparent concentrate.
4) yellow transparent concentrate two ends dialysis clamp is clipped in the dialysis bag that molecular weight is 3500Da, in 4 DEG C of darknesses
Under conditions of, dialyse 24h, changes a ultra-pure water per 8h, you can obtain the carbon quantum dot with grass carp scales as raw material.
(2) detect
1. the carbon quantum dot that will be obtained is diluted with ultra-pure water, and the multiple of dilution is 1:15, the carbon quantum dot solution of dilution is obtained,
Carry out detecting UV absorption wavelength, as a result such as Fig. 1.
As seen from Figure 1, a faint peak is seen at 290nm wavelength, a stronger purple is seen at 220nm wavelength
Outer absworption peak, can be obtained with ultraviolet spectrophotometry, the maximum absorption band of the carbon quantum dot prepared as raw material with grass carp scales,
Wavelength is 220nm.
2., by changing the excitation wavelength of luminoscope, from 320nm to 400nm, 10nm incremented by successively obtains corresponding to scope
Fluorescence emission spectrogram of compound, such as Fig. 2 a and Fig. 2 b.
The fluorescence intensity curves that comparison diagram 2a is obtained under the conditions of can be seen that different excitation wavelengths from Fig. 2 b are different, fluorescence
Intensity constantly strengthens with the rising of wavelength 320nm to 355nm, and in the case where 355nm wavelength is excited, fluorescence intensity reaches commanding elevation,
Then at wavelength 355nm to 400nm, fluorescence intensity declines with the increase of excitation wavelength.The excitation wavelength of portable uviol lamp
Usually 350nm to 360nm, the quantum dot can send fluorescence intensity higher, can be applied to room under this section of the exciting of wavelength
Outward, under field condition Mercury in Water Body ion direct detection, it is convenient and swift.
3. the carbon quantum dot that will be obtained carries out Fourier's infrared detection, as a result such as Fig. 3.
The present invention, Fourier's infrared spectrum of the carbon quantum dot prepared as raw material with grass carp scales shows, with grass carp scales
Be raw material prepare carbon quantum dot in 1656cm-1There is characteristic absorption peak at place, points out its surface with the presence of carboxyl, 3412cm-1Place has
Absworption peak, is hydroxyl peak, i.e., be can reach under unmodified nature with the carbon quantum dot that grass carp scales are prepared as raw material
It is preferably water-soluble；Especially in 627cm-1There is characteristic peak in place, points out the presence for having C-S keys, and sulfydryl take part in illustrating fish scale
Reaction, and generates C-S keys, is next step to Hg2+The great advantage of specific detection offer is provided.
4. the carbon quantum dot that will be obtained carries out X-ray powder diffraction detection, as a result such as Fig. 4.
From fig. 4, it can be seen that being illustrated with grass carp fish it can be found that there is characteristic diffraction peak at 23 ° by X powder diffraction figure
Squama is that its inside of carbon quantum dot prepared by raw material is the structure of the random arrangement of unordered carbon structure, i.e. carbon atom.
Application of carbon quantum dot of the embodiment 2 with fish scale as raw material in specific detection mercury ion
(1) influence of other metal ions
0.0150g Ni (NO are accurately weighed respectively3)2·6H2O, 0.0130g CuSO4·5H2O, 0.0145g Co
(NO3)2·6H2O, 0.0169g AgNO3, 0.0090g MnSO4, 0.0144g ZnSO4, 0.0140g FeCl3·6H2O,
0.0135g FeSO4·7H2O, 0.0830g Pb (NO3)2, 0.0200g Cr (NO3)3, 0.0154g Cd (NO3)2, 0.0158g
Ba(OH)2·8H2O, 0.0309g (NH4)6Mo7O24·4H2O, 0.0122g Bi (NO3)3·5H2Consolidate by totally 14 kinds of different metal salt for O
Body, is dissolved in ultra-pure water, is settled to 500mL, and respectively obtaining variant concentration of metal ions, to be 100 μM of metal ion molten
Liquid, places lucifuge shady place stand-by.
Carbon quantum dot prepared by embodiment 1 is diluted with ultra-pure water, and the multiple of dilution is 1:3, obtain the carbon quantum dot of dilution
Solution.
Carbon quantum dot solution is uniformly mixed with 100 μM of different metal ions solution respectively, volume ratio is 1:1, mixing
Uniformly, the carbon quantum dot that observation is prepared with grass carp scales as raw material is under other metal ion existence conditions to the shadow of fluorescence intensity
Ring.Result such as Fig. 5.
As shown in Figure 5, under conditions of the different metal ions in 50 μM of same concentrations are respectively present, Hg2+Addition make with
Grass carp scales are that carbon quantum dot solution fluorescence intensity prepared by raw material declines 1/2, and other metal ions almost do not have to fluorescence intensity
Have an impact, that uniquely have obvious fluorescence intensity decline is Cu2+, but quenching rate only reaches 1/4, is not enough to influence right
Hg2+Detection.Show, the cation coexisted in water body, and the same cycle, same to main group, element chemistry property has similitude
Metal ion will not produce interference, it was confirmed that the carbon quantum dot solution prepared as raw material with grass carp scales has to Hg2+Specifically
The potential quality of property detection probe.
(2) influence of intensity is quenched under condition of different pH to detection mercury ion.
Carbon quantum dot prepared by embodiment 1 is diluted with ultra-pure water, and the multiple of dilution is 1:1, obtain the carbon quantum dot of dilution
Solution.
It is that raw material prepares carbon quantum dot (CDs) solution to be picked with grass carp scales with glass bar, is dropped on accurate pH test paper, half
Compare with Standard colour board after second, pH value is about 6 to carbon quantum dot solution in itself, it is former to be adjusted respectively with NaOH solution with grass carp scales
Expect that the carbon quantum dot pH value of solution for preparing is 6.0,6.5,7.0,7.5,8.0,8.5,9.0.It is subsequently adding 50 μM of Hg2+Carry out fluorescence
Detection, as a result such as Fig. 6.
As seen from Figure 6, although fluorescence intensity quenching rate is different under condition of different pH, have no effect on probe acid and
To Hg in neutral environment2+Identification, illustrate the carbon quantum dot solution prepared as raw material with grass carp scales in weak acid and weak base, neutral pH
Under the conditions of mercury ion can be detected, the application in actual environment creates good condition.
(3) carbon quantum dot fluorescence intensity is influenceed under conditions of various concentrations mercury ion solution is present
Carbon quantum dot prepared by embodiment 1 is diluted with ultra-pure water, and the multiple of dilution is 1:1, obtain the carbon quantum dot of dilution
Solution.
It is by volume 1 with the mercury ion solution of various concentrations:1 mixes with carbon quantum dot solution, is existed with fluorescent machine respectively
To Hg under 355nm wavelength2+Detected, recorded the Hg of various concentrations2+To the carbon quantum solution prepared as raw material with grass carp scales
The influence of fluorescence intensity, as a result such as Fig. 7.
As seen from Figure 7,0.5 μM of Hg of -300 μM of concentration is added2+When, fluorescence intensity is declined slightly；As the Hg for adding2+It is dense
Spend for 40 μM when, fluorescence intensity is decreased obviously, that is, be quenched efficiency it is obvious；It will be clear that with Hg2+The liter of concentration
Height, fluorescence intensity constantly declines, quenching efficiency enhancing, works as Hg2+When concentration is 300 μM, fluorescence intensity drops to original 1/2.
Claims (6)
1. a kind of carbon quantum dot with fish scale as raw material, it is characterised in that preparation method is as follows：
(1) fish scale is cleaned, is dried, shredded；
(2) after fish scale is mixed with ultra-pure water, it is transferred in reactor, is put into rupture pressure disc, seal, is then placed in Microwave Water heat seal
Cheng Yizhong, heating using microwave obtains suspension；
(3) suspension is stood, is cooled to room temperature, filter to take filtrate, obtain concentrate；
(4) concentrate two ends dialysis clamp is clipped in dialysis bag, under conditions of 4 DEG C of darknesses, dialyse 24h, is changed once per 8h
Ultra-pure water, obtains carbon quantum dot.
2. according to a kind of carbon quantum dot with fish scale as raw material described in claim 1, it is characterised in that：Fish scale and ultra-pure water
Solid-to-liquid ratio is 1g:70-90mL.
3. according to a kind of carbon quantum dot with fish scale as raw material described in claim 1, it is characterised in that：In microwave attenuation materials
In instrument, seven stages of heating using microwave point：First stage is warming up to 120 DEG C in 10min；Second stage is in 120 DEG C of constant temperature 5min；The
Three stages were warming up to 150 DEG C in 10min；Fourth stage is in 150 DEG C of constant temperature 5min；5th stage was warming up to 180 DEG C in 10min；
6th stage is in 180 DEG C of constant temperature 5min；7th stage was the stage of reaction, and reaction temperature is 210 DEG C, heats 2h；Microwave Water heat seal
Set into instrument parameter, power is 1000W, and upper pressure limit is 1.500MPa.
4. according to a kind of carbon quantum dot with fish scale as raw material described in claim 1, it is characterised in that：The molecular weight of dialysis bag
It is 3500Da.
5. application of any described carbon quantum dots with fish scale as raw material of claim 1-4 in specific detection mercury ion.
6. according to the application described in claim 5, it is characterised in that method is as follows：It is under normal temperature and pressure conditionses, mercury to be measured is molten
Liquid and carbon quantum dot solution 1:1 mixing, with ultra violet lamp, whether observation fluorescence is quenched.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955603A (en) * | 2017-11-28 | 2018-04-24 | 广东工业大学 | A kind of water-solubility fluorescent carbon quantum dot and preparation method thereof and a kind of method for detecting fructose |
| CN108562564A (en) * | 2018-03-29 | 2018-09-21 | 青岛大学 | A kind of carbon quantum dot and preparation method and application for the detection of dextrase activity |
| CN110079310A (en) * | 2019-04-28 | 2019-08-02 | 新乡医学院 | A method of carbon quantum dot with high fluorescence quantum yield is prepared by predecessor of aquatic products waste |
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| CN108562564A (en) * | 2018-03-29 | 2018-09-21 | 青岛大学 | A kind of carbon quantum dot and preparation method and application for the detection of dextrase activity |
| US10383976B1 (en) | 2018-10-08 | 2019-08-20 | King Saud University | Method of fabricating nanostructures from fish waste |
| CN110079310A (en) * | 2019-04-28 | 2019-08-02 | 新乡医学院 | A method of carbon quantum dot with high fluorescence quantum yield is prepared by predecessor of aquatic products waste |
| CN110079309A (en) * | 2019-04-28 | 2019-08-02 | 新乡医学院 | A kind of green synthesis method of blue-light-emitting carbon quantum dot |
| CN110316718A (en) * | 2019-06-28 | 2019-10-11 | 重庆文理学院 | A kind of pair of transmitting red fluorescence carbon quantum dot and preparation method thereof |
| CN110316718B (en) * | 2019-06-28 | 2021-04-06 | 重庆文理学院 | Double-emission red fluorescent carbon quantum dot and preparation method thereof |
| CN112239668A (en) * | 2020-07-15 | 2021-01-19 | 湖南师范大学 | Fluorescent carbon nano-particles and preparation method and application thereof |
| CN112239668B (en) * | 2020-07-15 | 2022-12-27 | 湖南师范大学 | Fluorescent carbon nano-particles and preparation method and application thereof |
| CN114214064A (en) * | 2021-12-20 | 2022-03-22 | 重庆文理学院 | Biomass carbon quantum dot and preparation method thereof |
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