CN107421932A - Utilize the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI - Google Patents
Utilize the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI Download PDFInfo
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Abstract
The invention discloses a kind of method using nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI, including：Step 1: Cr VI is mixed with PBS cushioning liquid, instill sodium nitrite solution, positive electrode output end and negative electrode input are placed under liquid level again, sexavalence chromium standard solution is prepared by electric current, nitrogen phosphorus doping carbon quantum dot and PBS cushioning liquid are mixed, freeze 30min, it is ultrasonically treated, 30min is freezed again, again nitrogen phosphorus doping carbon quantum dot solution is prepared with ultraviolet irradiation, the sexavalence chromium standard solution of various concentrations is added thereto, irradiates exciting light, establishes the relation of hexavalent chromium concentration and fluorescence intensity；Step 2: irradiation exciting light, detects fluorescence intensity corresponding to solution to be measured, according to the hexavalent chromium concentration and the relation of fluorescence intensity detected in step 1, the concentration of corresponding Cr VI in solution to be measured is read.The present invention, which has, detects the high beneficial effect of sensitive, strong antijamming capability, accuracy in detection.
Description
Technical field
The present invention relates to Cr VI detection field.It is more particularly related to a kind of utilize nitrogen phosphorus doping carbon quantum
The method that point probe detects Cr VI.
Background technology
In the past few decades, with the fast development of industry, the harmful substance being discharged into environment is continuously increased.Such as
Cr (VI), Cr (VI) have carcinogenicity, to the very harmful of the mankind, therefore, work out a kind of energy simply, efficiently method goes to examine
The Cr (VI) surveyed in environment has great importance.According to the regulation of Environmental Protection Agency：Maximum allowable Cr (VI) in drinking water
Concentration is 0.1mg/L, in order to detect and ensure the quality of drinking water, reduces the discharge capacity of harmful substance, is badly in need of one kind and possesses choosing
Selecting property is good, high sensitivity and energy quick detection low concentration Cr (VI) analysis method.According to known report, existing many scientific researches
The method that researcher investigated Cr (VI) in the different sample substrates of many detections, including including chromatography, Atomic absorption
Spectroscopic methodology etc..But the equipment that the detection method in these reports is required for costliness mostly, complicated sample pretreatment and choosing
Selecting property and sensitivity are all undesirable.Therefore, work out one it is simple, and with good selectivity and highly sensitive side
Method, it is significant for Cr (VI) detections.
Science and technology is developed rapidly so that applications to nanostructures and research and development are swift and violent, and wherein fluorescent nano material is because having
The general character and the outstanding fluorescence property of common nano material and be widely used in the field such as biology, chemistry, medical science.Often
The fluorescent nano material seen have quantum dot (Quantum dots, QDs), metal-doped fluorescent nano material, metal nanometre cluster,
Composite organic-inorganic material etc..Quantum dot is again because it has narrow transmitting peak shape, width and continuous absorption spectrum, easily controllable
Launch wavelength the advantages that, it is widely used in fields such as biochemistry, biology, materia medica.But due to itself
Containing heavy metal ion, very important injury can all be caused to environment and human body, limit its application in each field.2004
Year, a kind of fluorescent material is found, and thereafter, by a series of research, carbon point (Carbon dots) formally turns into this new
The title of fluorescent nano material.Relative to the material of other same types, carbon point is so that raw material is cheap and easy to get, hypotoxicity, bio-compatible
Property, the advantages that good water solubility, chemical property are stable and obtained extensively in fields such as biochemistry, biological medicine, analytical chemistry
General application.In the recent period, the research day that the heavy metal ion and biomolecule using the property of carbon point fluorescence as foundation are measured
Benefit increases.The detection in ion and molecule, cell imaging etc. are applied carbon point, in the field such as biology, chemistry, material
There are good development prospect and wide development space.
It is above-mentioned when existing in solution but the detection of Cr VI is vulnerable to ferric iron, trivalent chromium and molybdic interference
During material, testing result is often inaccurate, and the above-mentioned substance in environment is generally existing, therefore research one kind can be examined sensitively
The concentration of Cr VI is measured, and the interference of environmental factor can be avoided, the concentration for preparing to measure Cr VI is significant.
The content of the invention
It is an object of the invention to solve at least the above, and provide the advantages of at least will be described later.
, can be with it is a still further object of the present invention to provide the method using nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI
Cr VI sensitively is detected, accurately and reliably detects the concentration of Cr VI in solution, strong antijamming capability.
In order to realize according to object of the present invention and further advantage, there is provided one kind utilizes nitrogen phosphorus doping carbon quantum dot
The method of probe in detecting Cr VI, comprises the following steps：
Step 1: preparing nitrogen phosphorus doping carbon quantum dot, nitrogen phosphorus doping carbon quantum dot solution is prepared, addition is different dense thereto
The sexavalence chromium standard solution of degree, exciting light is irradiated, establish the relation of hexavalent chromium concentration and fluorescence intensity；
Step 2: irradiation exciting light, detects fluorescence intensity corresponding to the solution to be measured containing Cr VI, according in step 1
The hexavalent chromium concentration of detection and the relation of fluorescence intensity, read the concentration of corresponding Cr VI in solution to be measured.
Preferably, hexavalent chromium concentration is established in step 1 and the relation of fluorescence intensity is specially：Detect every part of Cr VI
Fluorescence spectrum corresponding to standard liquid, and record fluorescence intensity corresponding to every part of sexavalence chromium standard solution, using concentration as 0 sexavalence
The ratio of the fluorescence intensity corresponding with the sexavalence chromium standard solution of the other concentration of any part of fluorescence intensity corresponding to chromium standard solution
For ordinate, the concentration of every part of sexavalence chromium standard solution is abscissa, draws standard curve and accounting equation；
Step 2 is specially：Solution to be measured containing Cr VI is added in a nitrogen phosphorus doping carbon quantum dot solution,
Exciting light is irradiated, detects fluorescence spectrum corresponding to solution to be measured, and fluorescence intensity corresponding to recording solution to be measured, substitute into the side
Journey obtains the concentration of corresponding Cr VI in solution to be measured.
Preferably, the wavelength of exciting light is 380nm.
Preferably, use pH for 7.4 PBS buffer preparation nitrogen phosphorus doping carbon quantum dot solution and Cr VI standard
Solution, pH is used to adjust the pH value of solution to be measured to 7.4 for 7.4 PBS cushioning liquid.
Preferably, the concentration of nitrogen phosphorus doping carbon quantum dot standard liquid is 0.5mg/mL.
Preferably, the preparation method of nitrogen phosphorus doping carbon quantum dot is specially：
S1, hydrotalcite crushed to 120 mesh sieves, be placed in tartaric acid successively at 30 DEG C, 60 DEG C, 90 DEG C and 30 DEG C
Heating water bath, water bath time are respectively 10min, 20min, 30min and 10min, filtering, it is heavy to be washed with deionized first
Starch 3 times, 20~30min of supersound process in the carbon tetrachloride solution of soybean lecithin is placed in, filtering, is washed with deionized second
Sediment 3 times, it is placed under infrared ray and irradiates 15min, obtain modified hydrotalcite, wherein, supersonic frequency 400kHz, ultrasonic temperature is
80 DEG C, the mass volume ratio of soybean lecithin and carbon tetrachloride is 1g:20~50ml；
S2, modified hydrotalcite, 0.2g glutathione and 50mL mass fractions in 0.15g steps S1 is taken to be 45%
Phosphoric acid solution is dissolved in 250mL anaerobic high purity waters, and 1.5mL mass is added under conditions of 200r/min stirs and be passed through nitrogen
Fraction is 85% glucosamine solution, and mixture is produced after continuing 1h；
S3, by the mixture in step S2 in heated under vacuum to 650 DEG C, vacuum calcining 4.5h, be cooled to room temperature,
It is placed in again in the hydrochloric acid solution that mass fraction is 40%, stirs 4.5h under nitrogen protection, nitrogen phosphorus doping is obtained after high speed centrifugation
Carbon quantum dot.
Preferably,
Preparing nitrogen phosphorus doping carbon quantum dot solution is specially：Nitrogen phosphorus doping carbon quantum dot and PBS cushioning liquid are pressed into quality
Volume ratio is 0.5mg:After 1mL mixing, less than 0 DEG C freezing 30min is placed in, is ultrasonically treated, is then placed in less than 0 DEG C freezing again
30min, it is placed under ultraviolet and irradiates 5min, stands until recovering normal temperature, wherein, supersonic frequency 40kHz, ultrasonic temperature
For 20 DEG C, ultrasonic time 10min.
Preferably,
The compound method of sexavalence chromium standard solution is specially：Cr VI is mixed with PBS cushioning liquid, under stirring
The sodium nitrite solution that mass fraction is 0.1% is instilled, then positive electrode output end and negative electrode input are placed under liquid level,
Pass through 5mA electric current, conduction time 10min；
Solution to be measured containing Cr VI is also pre-processed, and is specially：Solution to be measured is adjusted with PBS cushioning liquid
PH value is 7.4, instills the sodium nitrite solution that mass fraction is 0.1% under stirring, then by positive electrode output end and
Negative electrode input is placed under liquid level, by 5mA electric current, after energization 10min；
Wherein, the volume ratio of sodium nitrite solution and PBS cushioning liquid is 0.1:1.
Preferably, the concentration of the sexavalence chromium standard solution of more parts of various concentrations in step 1 is followed successively by：0、1×10- 6mol/L、3×10-6mol/L、5×10-6mol/L、7×10-6mol/L、9×10-6mol/L、1.2×10-5mol/L、1.5×
10-5mol/L、1.8×10-5mol/L、2.1×10-5mol/L、2.4×10-5mol/L、2.7×10-5mol/L、3.0×10- 5mol/L、3.3×10-5mol/L、3.6×10-5Mol/L and 3.9 × 10-5mol/L。。
The present invention comprises at least following beneficial effect：
Firstth, the advantages of detection method of the invention has high sensitivity, strong antijamming capability, detection accurately and reliably；
Secondth, can be learnt from fluorescence spectra, hexavalent chromium concentration is that fluorescence intensity corresponding to 0 is corresponding with solution to be detected
Fluorescence intensity increase with the increase of the concentration of Cr VI, and the concentration of fluorescence intensity ratio and Cr VI have it is good linear
Relation；
3rd, hydrotalcite crushed to 120 mesh sieves, is placed in tartaric acid successively at 30 DEG C, 60 DEG C, 90 DEG C and 30 DEG C
Lower heating water bath, water bath time are respectively 10min, 20min, 30min and 10min, filtering, are washed with deionized first
Sediment 3 times so that the particle diameter of the first sediment is more uniform, small, is placed in the carbon tetrachloride solution of soybean lecithin at ultrasound
20~30min is managed, filtering, the second sediment is washed with deionized 3 times, dissolves the trickle feeler knot stretched out in particle
Structure, it is placed under infrared ray and irradiates 15min, infrared ray continues to remove less soluble feeler structure, and it is uniform to obtain particle, structure phase
As modified hydrotalcite powder, reduce intergranular otherness, then with glutathione, phosphoric acid solution is molten, anaerobic high purity water mixes,
200r/min adds the glucosamine solution that 1.5mL mass fractions are 85% under conditions of stirring and being passed through nitrogen, obtains
Mixture containing nitrogen phosphorus doping carbon quantum dot, nitrogen, phosphorus, the electron cloud of carbon, in the structure of similar triangle, it is vacuum condition
Under be heated to 650 DEG C, vacuum calcining 4.5h, be cooled to room temperature, then be placed in mass fraction be 40% hydrochloric acid solution in, in nitrogen
The lower stirring 4.5h of protection, high speed centrifugation eliminate impurity, obtain purer nitrogen phosphorus doping carbon quantum dot；
4th, after mixing nitrogen phosphorus doping carbon quantum dot and PBS cushioning liquid, less than 0 DEG C freezing 30min, ultrasound are placed in
Processing, less than 0 DEG C freezing 30min is then placed in again, is placed under ultraviolet and irradiates 5min, nitrogen phosphorus doping carbon quantum dot is molten in PBS
Deploy in liquid, in the presence of hydrogen ion and hydroxide ion, and under ultraviolet irradiation, nitrogen, phosphorus, carbon location movement, drive
Electron cloud structural shift, class obtuse triangle shape is formed, carbon atom is located near obtuse angle, and electron cloud is concentrated at obtuse angle, is easy to
Receive exciting light, and change into fluorescent emission；
5th, Cr VI is mixed with PBS cushioning liquid, instills the nitrous that mass fraction is 0.1% under stirring
Acid sodium solution, then positive electrode output end and negative electrode input are placed under liquid level, by 5mA electric current, conduction time is
10min so that electronics is free in outermost, and hexavalent chromium completely reveals, and shows strong electric polarity, has superpower match somebody with somebody
Position performance.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings
Fig. 1 is the fluorescence spectra of the sexavalence chromium standard solution of the present invention；
Fig. 2 is the fluorescence intensity ratio of the present invention and the canonical plotting of hexavalent chromium concentration.
Embodiment
With reference to embodiment, the present invention is described in further detail, to make those skilled in the art with reference to specification
Word can be implemented according to this.
<Embodiment 1>
A kind of method using nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI, comprise the following steps：
Step 1: the nitrogen phosphorus doping carbon quantum dot for using pH to be 0.5mg/mL for 7.4 PBS buffer preparation concentration is molten
Liquid, pH is used to configure the sexavalence chromium standard solution of more parts of various concentrations for 7.4 PBS cushioning liquid, sexavalence chromium standard solution
Concentration is followed successively by：0、1×10-6mol/L、3×10-6mol/L、5×10-6mol/L、7×10-6mol/L、9×10-6mol/L、
1.2×10-5mol/L、1.5×10-5mol/L、1.8×10-5mol/L、2.1×10-5mol/L、2.4×10-5mol/L、2.7×
10-5mol/L、3.0×10-5mol/L、3.3×10-5mol/L、3.6×10-5mol/L、3.9×10-5mol/L、4.2×10- 5mol/L、4.5×10-5Mol/L and 4.8 × 10-5Mol/L, the nitrogen phosphorus doping carbon quantum that 19 parts of volumes are 3ml is measured respectively
Solution is put, adds a sexavalence chromium standard solution in a nitrogen phosphorus doping carbon quantum dot solution respectively, illumination wavelength is 380nm's
Exciting light, the fluorescence spectra of transmitting light as shown in Figure 1 is obtained, and record 480nm corresponding to every part of sexavalence chromium standard solution
Fluorescence intensity, six using concentration as 480nm fluorescence intensity corresponding to 0 sexavalence chromium standard solution and the other concentration of any part
The ratio of 480nm fluorescence intensity corresponding to valency chromium standard solution is ordinate, and the concentration of every part of sexavalence chromium standard solution is horizontal stroke
Coordinate, as shown in Figure 2, the concentration of sexavalence chromium standard solution is 0~3.9 × 10-5During mol/L, fluorescence intensity ratio and sexavalence
The concentration of chromium has good linear relationship, draws standard curve and accounting equation；；
Step 2: it is 7.4 PBS cushioning liquid by the pH value of the solution to be measured containing Cr VI regulation to 7.4 to use pH,
Solution to be measured is added in the nitrogen phosphorus doping carbon quantum dot solution that a volume is 3ml, illumination wavelength is exciting for 380nm
Light, fluorescence spectrum corresponding to solution to be measured is detected, and record the fluorescence intensity of 480nm corresponding to solution to be measured, substitute into the side
Journey obtains the concentration of corresponding Cr VI in solution to be measured.
<Embodiment 2>
Determination step with embodiment 1, wherein, unlike the preparation method of nitrogen phosphorus doping carbon quantum dot, nitrogen in step 1
The compound method of phosphorus doping carbon quantum dot solution, the compound method of sexavalence chromium standard solution and to be measured molten containing Cr VI
The pretreatment of liquid is different, described in detail below：
The preparation method of nitrogen phosphorus doping carbon quantum dot is specially：
S1, hydrotalcite crushed to 120 mesh sieves, be placed in tartaric acid successively at 30 DEG C, 60 DEG C, 90 DEG C and 30 DEG C
Heating water bath, water bath time are respectively 10min, 20min, 30min and 10min, filtering, it is heavy to be washed with deionized first
Starch 3 times, 20~30min of supersound process in the carbon tetrachloride solution of soybean lecithin is placed in, filtering, is washed with deionized second
Sediment 3 times, it is placed under infrared ray and irradiates 15min, obtain modified hydrotalcite, wherein, supersonic frequency 400kHz, ultrasonic temperature is
80 DEG C, the mass volume ratio of soybean lecithin and carbon tetrachloride is 1g:20~50ml；
S2, modified hydrotalcite, 0.2g glutathione and 50mL mass fractions in 0.15g steps S1 is taken to be 45%
Phosphoric acid solution is dissolved in 250mL anaerobic high purity waters, and 1.5mL mass is added under conditions of 200r/min stirs and be passed through nitrogen
Fraction is 85% glucosamine solution, and mixture is produced after continuing 1h；
S3, by the mixture in step S2 in heated under vacuum to 650 DEG C, vacuum calcining 4.5h, be cooled to room temperature,
It is placed in again in the hydrochloric acid solution that mass fraction is 40%, stirs 4.5h under nitrogen protection, nitrogen phosphorus doping is obtained after high speed centrifugation
Carbon quantum dot.
Preparing nitrogen phosphorus doping carbon quantum dot solution is specially：Nitrogen phosphorus doping carbon quantum dot and PBS cushioning liquid are pressed into quality
Volume ratio is 0.5mg:After 1mL mixing, less than 0 DEG C freezing 30min is placed in, is ultrasonically treated, is then placed in less than 0 DEG C freezing again
30min, it is placed under ultraviolet and irradiates 5min, stands until recovering normal temperature, wherein, supersonic frequency 40kHz, ultrasonic temperature
For 20 DEG C, ultrasonic time 10min.
The compound method of sexavalence chromium standard solution is specially：Cr VI is mixed with PBS cushioning liquid, under stirring
The sodium nitrite solution that mass fraction is 0.1% is instilled, then positive electrode output end and negative electrode input are placed under liquid level,
Pass through 5mA electric current, conduction time 10min；
Solution to be measured containing Cr VI is also pre-processed, and is specially：Solution to be measured is adjusted with PBS cushioning liquid
PH value is 7.4, instills the sodium nitrite solution that mass fraction is 0.1% under stirring, then by positive electrode output end and
Negative electrode input is placed under liquid level, by 5mA electric current, after energization 10min；
Wherein, the volume ratio of sodium nitrite solution and PBS cushioning liquid is 0.1:1.
<Comparative example 1>
Using the concentration of Cr VI in colorimetric determination solution to be measured, wherein, 16 parts of preparation is to be measured molten containing Cr VI
Liquid, the concentration of Cr VI is respectively 2 × 10 in the solution to be measured containing Cr VI-6mol/L、1×10-5mol/L、1.6×10- 5Mol/L and 3.5 × 10-5Mol/L, it is divided into totally 4 groups of A, B, C and D, every group 4 parts, trivalent is added into B groups solution to be measured
Iron, it is finally 5 × 10 to make ferric concentration in solution to be measured-6Mol/L, obtain 4 parts and contain Cr VI and ferric to be measured
Solution, sexavalence molybdenum is added into C groups solution to be measured, it is finally 1 × 10 to make the molybdic concentration of concentration in solution to be measured-5Mol/L,
Obtain 4 parts and contain Cr VI and molybdic solution to be measured, add trivalent chromium into D groups solution to be measured, make three in solution to be measured
The concentration of valency chromium is 1 × 10-65Mol/L, obtain the solution to be measured containing Cr VI and trivalent chromium.
<Comparative example 2>
Determination step with embodiment 1, wherein, solution to be measured containing Cr VI is different, and the compound method of solution to be measured is same
Comparative example 1.
<Comparative example 3>
Determination step with embodiment 2, wherein, solution to be measured containing Cr VI is different, and the compound method of solution to be measured is same
Comparative example 1.
<Testing result>
It is as shown in table 1 Cr VI testing result：
The detection limit of the Cr VI of embodiment 1 and embodiment 2 is substantially less than comparative example 1 as can be seen from Table 1, illustrates to use
The sensitivity of the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI is apparently higher than colorimetric method, and comparative example 1 is to B groups, C groups, D
The Detection accuracy of Cr VI is below 90% in group, illustrates that the detection of colorimetric method is vulnerable to ferric iron, sexavalence molybdenum and trivalent chromium
Interference, have a strong impact on the degree of accuracy；
Comparative example 2 is above 95% to the Detection accuracy of B groups and the Cr VI of C groups, and the detection to the Cr VI of D groups is accurate
True rate only has 81.09%, illustrates the method using nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI in embodiment 1, can be with
Ferric iron and molybdic interference are eliminated, so as to avoid influenceing detection accuracy, but the interference of trivalent chromium can not be eliminated, so
Cause D group Detection accuracies low；
Comparative example 3 more than 99%, illustrates embodiment 2 to the Detection accuracy of the Cr VI of B groups, C groups and D groups
In the method using nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI, ferric iron, sexavalence molybdenum and trivalent chromium can be eliminated
Interference, so as to accurately detect the concentration of Cr VI.
Number of devices and treatment scale described herein are the explanations for simplifying the present invention.To the present invention application,
Modifications and variations will be readily apparent to persons skilled in the art.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, it is of the invention and unlimited
In specific details and shown here as the legend with description.
Claims (9)
- A kind of 1. method using nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI, it is characterised in that comprise the following steps：Step 1: preparing nitrogen phosphorus doping carbon quantum dot, nitrogen phosphorus doping carbon quantum dot solution is prepared, adds various concentrations thereto Sexavalence chromium standard solution, exciting light is irradiated, establish the relation of hexavalent chromium concentration and fluorescence intensity；Step 2: irradiation exciting light, detect the solution to be measured containing Cr VI corresponding to fluorescence intensity, detected according in step 1 Hexavalent chromium concentration and fluorescence intensity relation, read the concentration of corresponding Cr VI in solution to be measured.
- 2. the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI is utilized as claimed in claim 1, it is characterised in that step The relation that hexavalent chromium concentration and fluorescence intensity are established in rapid one is specially：Detect fluorescence light corresponding to every part of sexavalence chromium standard solution Spectrum, and fluorescence intensity corresponding to every part of sexavalence chromium standard solution is recorded, using concentration as fluorescence corresponding to 0 sexavalence chromium standard solution The ratio of intensity fluorescence intensity corresponding with the sexavalence chromium standard solution of the other concentration of any part is ordinate, every part of Cr VI mark The concentration of quasi- solution is abscissa, draws standard curve and accounting equation；Step 2 is specially：Solution to be measured containing Cr VI is added in a nitrogen phosphorus doping carbon quantum dot solution, irradiated Exciting light, fluorescence spectrum corresponding to solution to be measured is detected, and fluorescence intensity corresponding to recording solution to be measured, substitute into the equation and obtain The concentration of corresponding Cr VI into solution to be measured.
- 3. the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI is utilized as claimed in claim 1, it is characterised in that swash Luminous wavelength is 380nm.
- 4. the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI is utilized as claimed in claim 1, it is characterised in that adopt With the PBS buffer preparation nitrogen phosphorus doping carbon quantum dot solution and sexavalence chromium standard solution that pH is 7.4, pH is used as 7.4 PBS cushioning liquid adjusts the pH value of solution to be measured to 7.4.
- 5. the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI is utilized as claimed in claim 1, it is characterised in that nitrogen The concentration of phosphorus doping carbon quantum dot standard liquid is 0.5mg/mL.
- 6. the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI is utilized as claimed in claim 1, it is characterised in that nitrogen The preparation method of phosphorus doping carbon quantum dot is specially：S1, hydrotalcite crushed to 120 mesh sieves, be placed in tartaric acid the water-bath at 30 DEG C, 60 DEG C, 90 DEG C and 30 DEG C successively Heating, water bath time are respectively 10min, 20min, 30min and 10min, filtering, the first sediment 3 are washed with deionized It is secondary, 20~30min of supersound process in the carbon tetrachloride solution of soybean lecithin is placed in, filtering, the second precipitation is washed with deionized Thing 3 times, it is placed under infrared ray and irradiates 15min, obtain modified hydrotalcite, wherein, supersonic frequency 400kHz, ultrasonic temperature 80 DEG C, the mass volume ratio of soybean lecithin and carbon tetrachloride is 1g:20~50ml；S2, take the phosphoric acid that modified hydrotalcite, 0.2g glutathione and 50mL mass fractions in 0.15g steps S1 are 45% Solution is dissolved in 250mL anaerobic high purity waters, and 1.5mL mass fractions are added under conditions of 200r/min stirs and be passed through nitrogen For 85% glucosamine solution, mixture is produced after continuing 1h；S3, by the mixture in step S2 in heated under vacuum to 650 DEG C, vacuum calcining 4.5h, be cooled to room temperature, then put In the hydrochloric acid solution that mass fraction is 40%, 4.5h is stirred under nitrogen protection, nitrogen phosphorus doping carbon amounts is obtained after high speed centrifugation Sub- point.
- 7. the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI is utilized as claimed in claim 4, it is characterised in thatPreparing nitrogen phosphorus doping carbon quantum dot solution is specially：Nitrogen phosphorus doping carbon quantum dot and PBS cushioning liquid are pressed into quality volume Than for 0.5mg:After 1mL mixing, less than 0 DEG C freezing 30min is placed in, is ultrasonically treated, be then placed in less than 0 DEG C freezing 30min again, It is placed under ultraviolet and irradiates 5min, stands until recovering normal temperature, wherein, supersonic frequency 40kHz, ultrasonic temperature 20 DEG C, ultrasonic time 10min.
- 8. the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI is utilized as claimed in claim 4, it is characterised in thatThe compound method of sexavalence chromium standard solution is specially：Cr VI is mixed with PBS cushioning liquid, instilled under stirring Mass fraction is 0.1% sodium nitrite solution, and then positive electrode output end and negative electrode input are placed under liquid level, passed through 5mA electric current, conduction time 10min；Solution to be measured containing Cr VI is also pre-processed, and is specially：Solution to be measured is adjusted into pH value with PBS cushioning liquid For 7.4, the sodium nitrite solution that mass fraction is 0.1% is instilled under stirring, then by positive electrode output end and negative electricity Pole input is placed under liquid level, by 5mA electric current, after energization 10min；Wherein, the volume ratio of sodium nitrite solution and PBS cushioning liquid is 0.1:1.
- 9. the method for nitrogen phosphorus doping carbon quantum dot probe in detecting Cr VI is utilized as claimed in claim 1, it is characterised in that step The concentration of the sexavalence chromium standard solution of more parts of various concentrations in rapid one is followed successively by：0、1×10-6mol/L、3×10-6mol/L、5 ×10-6mol/L、7×10-6mol/L、9×10-6mol/L、1.2×10-5mol/L、1.5×10-5mol/L、1.8×10-5mol/ L、2.1×10-5mol/L、2.4×10-5mol/L、2.7×10-5mol/L、3.0×10-5mol/L、3.3×10-5mol/L、3.6 ×10-5Mol/L and 3.9 × 10-5mol/L。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108051415A (en) * | 2017-12-11 | 2018-05-18 | 河南省农业科学院农业质量标准与检测技术研究所 | A kind of method of ratio fluorescent detection hexavalent chromium |
| CN108489945A (en) * | 2018-03-19 | 2018-09-04 | 陕西科技大学 | It is a kind of to prepare the method and its application that carbon quantum dot detects hexavalent chromium based on gelatin |
| CN108956552A (en) * | 2018-05-02 | 2018-12-07 | 中国科学院化学研究所 | A kind of preparation method of carbon quantum dot and method with carbon quantum dot detection dichromate ion |
| CN114620710A (en) * | 2022-01-18 | 2022-06-14 | 陕西科技大学 | Synthesis method and application of fluorescent carbon quantum dot and nitrogen-phosphorus co-doped fluorescent carbon quantum dot |
| TWI805670B (en) * | 2018-01-02 | 2023-06-21 | 中國北京師範大學 | Triangular carbon quantum dots and compositions and uses thereof |
| CN116891739A (en) * | 2023-07-12 | 2023-10-17 | 长春工业大学 | Method for preparing phosphorus-doped carbon quantum dots by taking calcium gluconate as raw material and application of phosphorus-doped carbon quantum dots in hexavalent chromium ion detection |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106315557A (en) * | 2016-08-18 | 2017-01-11 | 常州大学 | Preparation method for nitrogen and phosphorus-doped carbon quantum dots |
-
2017
- 2017-07-26 CN CN201710617996.4A patent/CN107421932B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106315557A (en) * | 2016-08-18 | 2017-01-11 | 常州大学 | Preparation method for nitrogen and phosphorus-doped carbon quantum dots |
Non-Patent Citations (3)
| Title |
|---|
| XIAOJUAN GONG ET AL.: "An "on-off-on" fluorescent nanoprobe for recognition of chromium(VI) and ascorbic acid based on phosphorus/nitrogen dualdoped carbon quantum dot", 《ANALYTICA CHIMICA ACTA》 * |
| 曾强 等: "氮掺杂碳点的制备及在六价铬检测中的应用", 《化学与生物工程》 * |
| 陈文新 等: "基于生物质甘蔗渣的荧光碳量子点制备", 《暨南大学学报( 自然科学与医学版)》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108051415A (en) * | 2017-12-11 | 2018-05-18 | 河南省农业科学院农业质量标准与检测技术研究所 | A kind of method of ratio fluorescent detection hexavalent chromium |
| CN108051415B (en) * | 2017-12-11 | 2020-07-24 | 河南省农业科学院农业质量标准与检测技术研究所 | Method for detecting hexavalent chromium ions by fluorescence ratio |
| TWI805670B (en) * | 2018-01-02 | 2023-06-21 | 中國北京師範大學 | Triangular carbon quantum dots and compositions and uses thereof |
| CN108489945A (en) * | 2018-03-19 | 2018-09-04 | 陕西科技大学 | It is a kind of to prepare the method and its application that carbon quantum dot detects hexavalent chromium based on gelatin |
| CN108956552A (en) * | 2018-05-02 | 2018-12-07 | 中国科学院化学研究所 | A kind of preparation method of carbon quantum dot and method with carbon quantum dot detection dichromate ion |
| CN108956552B (en) * | 2018-05-02 | 2020-10-27 | 中国科学院化学研究所 | Preparation method of carbon quantum dots and method for detecting dichromate by using carbon quantum dots |
| CN114620710A (en) * | 2022-01-18 | 2022-06-14 | 陕西科技大学 | Synthesis method and application of fluorescent carbon quantum dot and nitrogen-phosphorus co-doped fluorescent carbon quantum dot |
| CN116891739A (en) * | 2023-07-12 | 2023-10-17 | 长春工业大学 | Method for preparing phosphorus-doped carbon quantum dots by taking calcium gluconate as raw material and application of phosphorus-doped carbon quantum dots in hexavalent chromium ion detection |
| CN116891739B (en) * | 2023-07-12 | 2024-04-30 | 长春工业大学 | Method for preparing phosphorus-doped carbon quantum dots by taking calcium gluconate as raw material and application of phosphorus-doped carbon quantum dots in hexavalent chromium ion detection |
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