CN105860967A - Fluorescent carbon dots and preparation method thereof and monitoring method for catalyzing p-nitrophenol degradation - Google Patents
Fluorescent carbon dots and preparation method thereof and monitoring method for catalyzing p-nitrophenol degradation Download PDFInfo
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- CN105860967A CN105860967A CN201610235327.6A CN201610235327A CN105860967A CN 105860967 A CN105860967 A CN 105860967A CN 201610235327 A CN201610235327 A CN 201610235327A CN 105860967 A CN105860967 A CN 105860967A
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000012544 monitoring process Methods 0.000 title claims abstract description 24
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 18
- 230000015556 catabolic process Effects 0.000 title abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000004699 copper complex Chemical class 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 58
- 229910052799 carbon Inorganic materials 0.000 claims description 58
- 238000001514 detection method Methods 0.000 claims description 34
- 239000012279 sodium borohydride Substances 0.000 claims description 22
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 22
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 claims description 16
- 238000002211 ultraviolet spectrum Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002189 fluorescence spectrum Methods 0.000 claims description 10
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 239000003269 fluorescent indicator Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000000825 ultraviolet detection Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000013028 emission testing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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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- B82Y40/00—Manufacture or treatment of nanostructures
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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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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Abstract
The invention discloses fluorescent carbon dots and a preparation method thereof and a monitoring method for catalyzing p-nitrophenol degradation. The preparation method comprises the steps that 1, ethylenediamine tetraacetic acid disodium salt, soluble copper salt and water are mixed to form an aqueous solution of a copper complex; 2, the aqueous solution of the copper complex is subjected to a hydrothermal reaction, filtered, centrifuged and dialyzed, centrifuged supernatant liquid is taken to be dialyzed, and liquid in a dialyzing bag is taken to prepare the fluorescent carbon dots. The fluorescent carbon dots prepared through the method can be used as a fluorescent indicator for synchronously monitoring the catalytic degradation process of p-nitrophenol to play a role in serving as a naked eye observation platform in the catalytic degradation process; in addition, the preparation method of the fluorescent carbon dots is simple and environmentally friendly.
Description
Technical field
The present invention relates to fluorescent carbon point, in particular it relates to a kind of fluorescent carbon point and preparation method thereof and urging
Change the monitoring method of p-nitrophenol degraded.
Background technology
P-nitrophenol as the great organic matter of the toxicity that content in serious pollution industrial wastewater is higher,
Its catalytic degradation method is limited to more complicated catalytic degradation method such as electrode method, absorption method, chemical oxygen always
Change method, photocatalytic oxidation etc., its process is often the longest and can produce raw material or product pollution.
The catalyst extreme portions being applied to catalytic degradation p-nitrophenol of document report is all one at present
Plant or various metals, reach, by more complicated catalytic reaction process, purpose of degrading.And Catalytic active phase
Bigger metal is often related to noble metal, there is certain environmental pollution.P-nitrophenol is as toxicity
The biggest environmental contaminants, it is most likely that accumulate in vivo, although conventional method can be to a certain degree
On by its catalytic degradation, but be the absence of its presence or absence of a kind of Simultaneous Monitoring and observe the side of catalysis overall process
Method.
Summary of the invention
It is an object of the invention to provide a kind of fluorescent carbon point and preparation method thereof and catalysis p-nitrophenol
The monitoring method of degraded, the fluorescent carbon point prepared by the method can be as Simultaneous Monitoring p-nitrophenol
The fluorescence indicator of catalytic degradation process uses, and then it is flat to play the bore hole observation as catalytic degradation process
The effect of platform；And this fluorescent carbon point preparation method is simple and environmentally friendly.
To achieve these goals, the invention provides the preparation method of a kind of fluorescent carbon point, including:
1) disodium EDTA, soluble copper salt and water are mixed to form the water-soluble of copper complex
Liquid；
2) aqueous solution of copper complex is carried out hydro-thermal reaction, filters, is centrifuged, dialyses, take centrifugal after
Supernatant liquor dialyse, take the liquid in bag filter with prepared fluorescent carbon point.
Present invention also offers a kind of fluorescent carbon point, this fluorescent carbon point is prepared by above-mentioned method.
Invention further provides a kind of monitoring method being catalyzed p-nitrophenol degraded, this monitoring method
For: p-nitrophenyl phenol solution, sodium borohydride solution and above-mentioned fluorescent carbon point are carried out catalytic degradation reaction,
And reaction system is carried out fluorescence spectrum detection or ultraviolet spectra detection；
Wherein, blank group includes p-nitrophenol, sodium borohydride and water.
By technique scheme, metallic copper doping is entered in carbon point by one-step method, makes by the present invention
The fluorescent carbon point that must prepare has catalysis activity and the fluorescence property of excellence, and then makes this fluorescent carbon point energy
Enough fluorescence indicators as Simultaneous Monitoring p-nitrophenol catalytic degradation process use, and then play conduct
The effect of the bore hole observation platform of catalytic degradation process；And this fluorescent carbon point preparation method is simple and to ring
Border is friendly.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of specification, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the fluorescent emission detection figure of fluorescent carbon point solution A 1 in detection example 1；
Fig. 2 is the high-resolution-ration transmission electric-lens detection figure of fluorescent carbon point solution A 1 in detection example 2；
Fig. 3 is the testing result statistical chart of Fig. 2；
Fig. 4 is the x-ray photoelectron spectroscopy detection figure of detection example 3 fluorescent carbon point solution A 1；
Fig. 5 is the ultraviolet spectra detection figure in application examples 1 about variable concentrations sodium borohydride solution；
Fig. 6 is the ultraviolet spectra detection figure in application examples 1 about different volumes carbon point solution；
Fig. 7 is the ultraviolet spectra detection figure of optimal conditions in application examples 1；
Fig. 8 is the one-level Linear equations of Fig. 7；
Fig. 9 is bore hole monitoring result statistical chart in application examples 1；
Figure 10 is fluorescence spectrum statistical chart in application examples 2；
Figure 11 is the one-level Linear equations of Figure 10.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of fluorescent carbon point, including:
1) disodium EDTA, soluble copper salt and water are mixed to form the water-soluble of copper complex
Liquid；
2) aqueous solution of copper complex is carried out hydro-thermal reaction, filters, is centrifuged, dialyses, take centrifugal after
Supernatant liquor dialyse, take the liquid in bag filter with prepared fluorescent carbon point.
Step 1 in above-mentioned preparation method) in, the consumption of each material can select in wide scope,
But so that the fluorescent carbon point prepared can have higher productivity, more excellent catalysis activity and fluorescence
Can, it is preferable that in step 1) in, relative to the disodium EDTA of 0.5g, soluble copper
The consumption of salt is 0.1-0.3g, and the consumption of water is 20-40mL；
In the present invention, the concrete kind of soluble copper salt can select, from cost in wide scope
Consider, it is preferable that one or more in copper chloride, copper nitrate and copper sulphate of soluble copper salt.
In above-mentioned preparation method, the actual conditions of mixing can select in wide scope, but in order to
Make disodium EDTA, the soluble copper salt can be the most soluble in water, it is preferable that mixing
At least meeting following condition: mixing temperature is 150-250 DEG C, incorporation time is 120-360min.
Step 2 in above-mentioned preparation method) in, the actual conditions of hydro-thermal reaction can be in wide scope
Select, but in order to improve reaction rate and productivity, it is preferable that hydro-thermal reaction at least meets following condition:
Reaction temperature is 150-250 DEG C, and the reaction time is 2-6h.
In the present invention, the model of bag filter can select in wide scope, but in order to by little molecule
Impurity is the most thorough, it is preferable that the aperture of bag filter is not less than 1000KDa；It is highly preferred that
The time of dialysis is 12-24h.
Present invention also offers a kind of fluorescent carbon point, this fluorescent carbon point is prepared by above-mentioned method.
Invention further provides a kind of monitoring method being catalyzed p-nitrophenol degraded, this monitoring method
For: p-nitrophenyl phenol solution, sodium borohydride solution and above-mentioned fluorescent carbon point are carried out catalytic degradation reaction,
And reaction system is carried out fluorescence spectrum detection or ultraviolet spectra detection；
Wherein, blank group includes p-nitrophenol, sodium borohydride and water.
In above-mentioned monitoring method, the actual conditions of catalytic degradation reaction can select in wide scope,
But for the ease of monitoring reaction course more accurately, it is preferable that below catalytic degradation reaction at least meets
Condition: reaction temperature is 20-25 DEG C, the reaction time is 0.5-4.5min.
In the present invention, the concentration of each raw material and consumption can select in wide scope, in order to
Obtain excellent fluorescence intensity and the intensity of ultraviolet spectra, it is preferable that the concentration of p-nitrophenyl phenol solution
It is 2 × 10-4-4×10-4Mol/L, the concentration of sodium borohydride solution is 0.03-0.12mol/L；And relative to
The p-nitrophenyl phenol solution of 1mL, the consumption of fluorescent carbon point is 0.5-2mL, the consumption of sodium borohydride solution
For 0.5-2mL；In blank group, the p-nitrophenyl phenol solution relative to 1mL, the consumption of water is
0.5-2mL, the consumption of sodium borohydride solution is 0.5-2mL.
In above-mentioned monitoring method, during fluorescence spectrum and ultraviolet spectra detection, detection wavelength can be
Change in wide scope, but in order to obtain the strongest spectral intensity, it is preferable that detect at fluorescence spectrum
In, detection wavelength is 330-350nm；In ultraviolet spectra detects, detection wavelength is 200-500nm.
Hereinafter will be described the present invention by embodiment.In following example, fluorescence spectrum is joined
Number is recorded by sepectrophotofluorometer (F-4500Hitachi), and ultraviolet spectra parameter is divided by ultraviolet-visible
Light photometer (U3010Hitachi) records, and high analyte transmission electron microscope detection parameter is by high-resolution transmission electricity
Mirror (HRTEM, JEOL-2010) records, and x-ray photoelectron spectroscopy detection parameter passes through X-ray spectral analysis
Instrument (AXIS-ULTRADLD) records.
Embodiment 1
1) 0.5g disodium ethylene diamine tetraacetate, 0.1g copper chloride and 30mL ultra-pure water are mixed at 25 DEG C
Close 1-2min and form the aqueous solution of copper complex；
2) aqueous solution of above-mentioned copper complex is carried out at hydro-thermal reaction 4h at 200 DEG C, filter, be centrifuged,
Dialysis, take centrifugal after supernatant liquor dialyse, (aperture of bag filter is not less than 1000KDa), take
Liquid in bag filter is with prepared fluorescent carbon point solution A 1.
Embodiment 2
Carry out preparing fluorescent carbon point solution A 2, the except for the difference that use of copper chloride according to the method for embodiment 1
Amount is 0.15g, and reaction temperature is 150 DEG C.
Embodiment 3
Carry out preparing fluorescent carbon point solution A 3, the except for the difference that use of copper chloride according to the method for embodiment 1
Amount is 0.20g, and reaction temperature is 250 DEG C.
Embodiment 4
Carry out preparing fluorescent carbon point solution A 4, the except for the difference that use of copper chloride according to the method for embodiment 1
Amount is 0.25g.
Embodiment 5
Carry out preparing fluorescent carbon point solution A 5, the except for the difference that use of copper chloride according to the method for embodiment 1
Amount is 0.30g.
Detection example 1
Above-mentioned fluorescent carbon point solution A 1 is carried out fluorescent emission detection under different excitation wavelengths, specifically ties
Fruit sees Fig. 1, as shown in Figure 1, when excitation wavelength is after 300nm is gradually increased to 460nm, launches
Wavelength the most correspondingly carries out regular blue shift.
Similarly, the fluorescent emission testing result of fluorescent carbon point solution A 2-A5 and fluorescent carbon point solution A 1
Testing result keep consistent；The fluorescent carbon point solution that wherein fluorescence property is optimum is A2.
Detection example 2
Above-mentioned fluorescent carbon point solution A 1 is carried out high-resolution-ration transmission electric-lens detection under different excitation wavelengths,
Concrete outcome is shown in Fig. 2 and 3, and Fig. 2 is high-resolution-ration transmission electric-lens detection figure, and Fig. 3 is the detection knot of Fig. 2
Really statistical chart, as shown in Figure 2, the fluorescent carbon point prepared has lattice clearly, for crystal structure, by
Fig. 3 understands, and the particle diameter of fluorescent carbon point is mainly 6-8nm.
Similarly, the high-resolution-ration transmission electric-lens testing result of fluorescent carbon point solution A 2-A5 and fluorescent carbon point
The testing result of solution A 1 keeps consistent.
Detection example 3
Above-mentioned fluorescent carbon point solution A 1 is being carried out x-ray photoelectron spectroscopy detection, and concrete outcome is shown in Fig. 4,
As shown in Figure 4, containing carbon, oxygen, nitrogen and four kinds of elements of copper in fluorescent carbon point.
Similarly, the high-resolution-ration transmission electric-lens testing result of fluorescent carbon point solution A 2-A5 and fluorescent carbon point
The testing result of solution A 1 keeps consistent.
Application examples 1
Preparation 3 × 10-4Mol/L p-nitrophenyl phenol solution and relative to p-nitrophenol solution concentration 50 times,
100 times, 200 times, 300 times, the sodium borohydride solution of 400 times, be designated as A, B, C, D.In than
Look ware adds p-nitrophenyl phenol solution 1mL, sodium borohydride solution 1mL and 1mL carbon point solution
A1, carries out timing while adding carbon point solution, carries out ultraviolet spectra detection simultaneously, and concrete outcome is shown in
Fig. 5, as shown in Figure 5, when p-nitrophenol and sodium borohydride concentration are than catalytic rate during for 1:300
The fastest.
Cuvette is separately added into p-nitrophenyl phenol solution 1mL, 9 × 10-2The sodium borohydride solution of mol/L
1mL, ultra-pure water 2mL, carry out ultraviolet detection, is designated as blank group；It is separately added in cuvette
P-nitrophenyl phenol solution 1mL, 9 × 10-2The sodium borohydride solution 1mL of mol/L, count respectively 0.1mL,
0.5mL, 1mL, 1.5mL, 2mL (density is 1g/mL) carbon point solution A 1 is experimental group, simultaneously
Carrying out timing, concrete outcome is shown in Fig. 6, it will be appreciated from fig. 6 that when copper volume is 1g, catalytic rate is the fastest.
Summary obtains optimum experimental condition proportioning, is i.e. separately added into 3 × 10 in cuvette-4Mol/L is to nitre
Base phenol solution 1mL, 9 × 10-2The sodium borohydride solution 1mL of mol/L, ultra-pure water 2mL, carry out purple
Outer detection, is designated as blank group；P-nitrophenyl phenol solution 1mL it is separately added in cuvette,
9×10-2The carbon point solution A 1 of the sodium borohydride solution 1mL, 1mL of mol/L is experimental group, carries out simultaneously
Timing also makees ultraviolet detection, and concrete outcome is shown in that Fig. 7-Fig. 9, Fig. 7 are ultraviolet spectra statistical chart, and Fig. 8 is
The one-level Linear equations of Fig. 7, Fig. 9 be bore hole monitoring result statistical chart (As time goes on, than
Yellow in look ware is gradually taken off, and the blue-fluorescence under uviol lamp gradually recovers)；As shown in Figure 7,
Catalytic reaction can complete in 4min30s；As shown in Figure 8, rate of catalysis reaction is 1.06 × 10-2s-1；
As shown in Figure 9, the fluorescence of carbon point along with catalytic reaction complete can obtain major part recovery, more important
Be available with this fluorescence signal change monitor catalytic reaction process.
Application examples 2
3 × 10 it are separately added in cuvette-4Mol/L p-nitrophenyl phenol solution 1mL, 9 × 10-2Mol/L's
Sodium borohydride solution 1mL, ultra-pure water 2mL, carry out ultraviolet detection, is designated as blank group；In colorimetric
P-nitrophenyl phenol solution 1mL it is separately added in ware, 9 × 10-2The sodium borohydride solution 1mL, 1mL of mol/L
Carbon point solution A 1 be experimental group, carry out simultaneously timing and make fluorescence spectrum detection, concrete outcome is shown in figure
10-Figure 11, Figure 10 are fluorescence spectrum statistical chart, and Figure 11 is the one-level Linear equations of Figure 10；By scheming
10 understand, when, under the exciting at 340nm wavelength, the fluorescence of carbon point can through 4min30s by minimum point
To be gone up significantly；As shown in Figure 11, the ultraviolet suction at fluorescence intensity change and 400nm place
Receive peak intensity change and have good linear relationship, y=11251.24501x-2299.02191 (R=0.98915).
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible combinations are illustrated by the present invention the most separately.
Additionally, can also be combined between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the preparation method of a fluorescent carbon point, it is characterised in that including:
1) disodium EDTA, soluble copper salt and water are mixed to form the water-soluble of copper complex
Liquid；
2) aqueous solution of described copper complex is carried out hydro-thermal reaction, filters, is centrifuged, dialyses, take from
Supernatant liquor after the heart is dialysed, and takes the liquid in bag filter with prepared fluorescent carbon point.
Preparation method the most according to claim 1, wherein, in step 1) in, relative to 0.5g
Described disodium EDTA, the consumption of described soluble copper salt is 0.1-0.3g, described water
Consumption is 20-40mL；
Preferably, one or more in copper chloride, copper nitrate and copper sulphate of described soluble copper salt；
It is highly preferred that described mixing at least meets following condition: mixing temperature is 150-250 DEG C, mixing
Time is 120-360min.
Preparation method the most according to claim 2, wherein, in step 2) in, described hydro-thermal is anti-
Should at least meet following condition: reaction temperature is 150-250 DEG C, the reaction time is 2-6h.
Preparation method the most according to claim 3, wherein, the aperture of described bag filter is not less than
1000KDa；
Preferably, the time of described dialysis is 12-24h.
5. a fluorescent carbon point, it is characterised in that described fluorescent carbon point is by appointing in claim 1-4
A described method of anticipating is prepared.
6. the monitoring method being catalyzed p-nitrophenol degraded, it is characterised in that described monitoring method
For: p-nitrophenyl phenol solution, sodium borohydride solution and fluorescent carbon point as claimed in claim 5 are carried out
Catalytic degradation reaction, and reaction system is carried out fluorescence spectrum detection or ultraviolet spectra detection；
Wherein, blank group includes p-nitrophenol, sodium borohydride and water.
Monitoring method the most according to claim 6, wherein, described catalytic degradation reaction is the fullest
Be enough to lower condition: reaction temperature is 20-25 DEG C, the reaction time is 0.5-4.5min.
8. according to the monitoring method described in claim 6 or 7, wherein, described p-nitrophenyl phenol solution
Concentration be 2 × 10-4-4×10-4Mol/L, the concentration of described sodium borohydride solution is 0.03-0.12mol/L；
And the p-nitrophenyl phenol solution relative to 1mL, the consumption of described fluorescent carbon point is 0.5-2mL, described
The consumption of sodium borohydride solution is 0.5-2mL；
In blank group, the p-nitrophenyl phenol solution relative to 1mL, the consumption of described water is
0.5-2mL, the consumption of described sodium borohydride solution is 0.5-2mL.
Monitoring method the most according to claim 8, wherein, in described fluorescence spectrum detects,
Detection wavelength is 330-350nm.
Monitoring method the most according to claim 8, wherein, in described ultraviolet spectra detects,
Detection wavelength is 200-500nm.
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