CN112811412A - Preparation method and application of carbon dot fluorescent tracer - Google Patents
Preparation method and application of carbon dot fluorescent tracer Download PDFInfo
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- CN112811412A CN112811412A CN202011620486.0A CN202011620486A CN112811412A CN 112811412 A CN112811412 A CN 112811412A CN 202011620486 A CN202011620486 A CN 202011620486A CN 112811412 A CN112811412 A CN 112811412A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 69
- 239000000700 radioactive tracer Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 22
- 239000012498 ultrapure water Substances 0.000 claims abstract description 22
- 238000000502 dialysis Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000000498 cooling water Substances 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 17
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 17
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 17
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 13
- 230000005764 inhibitory process Effects 0.000 abstract description 10
- 238000011161 development Methods 0.000 abstract description 2
- 239000008235 industrial water Substances 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 description 29
- 239000000203 mixture Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000007865 diluting Methods 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000003814 drug Substances 0.000 description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 7
- 238000003828 vacuum filtration Methods 0.000 description 7
- 239000005708 Sodium hypochlorite Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920006318 anionic polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
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Abstract
The invention belongs to the technical field of industrial water treatment, and particularly relates to a preparation method and application of a carbon dot fluorescent tracer. The preparation method of the carbon dot fluorescent tracer comprises the following steps: mixing citric acid and phosphate, grinding into powder, placing the powder raw material in a container for high-temperature heating reaction, cooling to room temperature after the reaction is finished, adding ultrapure water into the container, stirring and dissolving, removing insoluble impurities through suction filtration, and finally performing dialysis purification by using a dialysis bag to obtain the carbon dot fluorescent tracer, wherein the obtained carbon dot fluorescent tracer is applied to circulating cooling water. The method has the advantages of low cost of the adopted raw materials, simple and quick preparation method, green and environment-friendly synthesized carbon dots, no pollution, high fluorescence intensity and good corrosion inhibition performance. The invention not only enriches the types of fluorescent tracers, but also widens the application field of carbon dots and provides a new direction for the development of the fluorescent tracers.
Description
Technical Field
The invention belongs to the technical field of industrial water treatment, and particularly relates to a preparation method and application of a carbon dot fluorescent tracer.
Background
Scale and corrosion inhibitors are added into industrial circulating cooling water to prevent scaling and corrosion of pipelines and economic loss and operation trouble caused by the scaling and corrosion inhibitors. However, the effect of the scale and corrosion inhibitors is directly related to the concentration of the scale and corrosion inhibitors, so that the monitoring of the concentration of the medicament in the water body in the actual work has great significance. The method for detecting the concentration of the water treatment agent commonly used in the market is a colorimetric method, for example, the characteristic that the cationic dye is combined with the anionic polymer medicament to change the color or the characteristic that the cationic surfactant is combined with the anionic polymer medicament to generate insoluble particles uniformly distributed in water is utilized, and then the concentration of the anionic polymer is represented by measuring the absorbance. In addition, the concentration of the medicament is obtained by detecting the orthophosphoric acid or the total phosphorus of the medicament in water, and obviously, the method is only suitable for a phosphorus-containing formula, and a system for detecting the total phosphorus needs to use ultraviolet light to digest the organophosphorus, so that the operation is troublesome. The common defects of the above detection methods are that additional chemical reagents are required, the operation is troublesome, the colorimetric analysis system has poor reliability, frequent maintenance is required, and the system cost is high.
The fluorescent tracing medicament can well solve the problems, and has the advantages of simple and rapid operation, high sensitivity and high accuracy, thereby realizing the on-line monitoring and automatic dosing of the medicament. However, the currently used fluorescent tracer is troublesome in preparation process, has certain toxicity, is expensive and is not easy to degrade. Carbon Dots (CDs), also known as carbon quantum dots, are carbon-based zero-dimensional materials composed of dispersed spheroidal carbon particles with extremely small dimensions (below 10 nm). The carbon dots have excellent fluorescence performance, and compared with the traditional organic fluorescent dye, the carbon dots have a wide excitation wavelength range and a narrow emission wavelength range, namely, excitation light with any wavelength less than 10nm of the emission wavelength can be used for excitation; the emission peaks of the carbon points are narrow and symmetrical, the overlapping is small, and the interference is small; the carbon dots have strong fluorescence intensity and stability, and almost have no light fading phenomenon. In addition, the carbon dot preparation method is simple, has good water solubility, biocompatibility, low toxicity and environmental friendliness, and is a very economic, green and efficient fluorescent tracer. In addition, the carbon dots exist per se or the modified surface can carry a large number of polar groups, such as phosphonic acid groups, hydroxyl groups, carboxyl groups, amino groups and the like, and the groups can be adsorbed on the surface of the metal pipe through chemical action and physical action to form a protective film to inhibit metal corrosion, so that the fluorescent powder can also reduce the corrosion of the pipe while exerting the fluorescent property, thereby achieving the aim of killing two birds with one stone.
Based on the above, the invention prepares a novel carbon dot material with high fluorescence intensity, good stability and certain corrosion inhibition performance, and the carbon dot material is used in circulating cooling water to make up the defects.
Disclosure of Invention
The invention aims to provide a preparation method and application of a carbon dot fluorescent tracer, and solves the problems of high price, complex preparation process and poor environmental protection performance of the existing fluorescent tracer.
The realization process of the invention is as follows:
a preparation method of a carbon dot fluorescent tracer comprises the following steps: mixing citric acid and phosphate, grinding into powder, placing the powder raw material in a container for high-temperature heating reaction, cooling to room temperature after the reaction is finished, adding ultrapure water into the container, stirring for dissolving, removing insoluble impurities through suction filtration, and finally performing dialysis purification by using a dialysis bag to obtain the carbon dot fluorescent tracer.
Further, the phosphate is selected from one or a combination of two or more of diammonium hydrogen phosphate, dipotassium hydrogen phosphate, ammonium dihydrogen phosphate and potassium dihydrogen phosphate.
Further, the phosphate is diammonium hydrogen phosphate.
Further, the mass ratio of the citric acid to the phosphate is 1: (0.3-4.5).
Further, the mass ratio of the citric acid to the ultrapure water is 1: (25-240).
Further, the vessel for high-temperature heating reaction is a crucible with a lid.
Further, the heating temperature of the high-temperature heating reaction is 120-250 ℃, and the reaction time is 0.5-24 h.
Furthermore, the dialysis bag is a dialysis bag with the molecular weight cutoff of 500-3500.
The carbon dot fluorescent tracer prepared by the method.
The carbon dot fluorescent tracer is used as a fluorescent tracer in circulating cooling water.
The invention has the following positive effects:
the method has the advantages of low cost of the adopted raw materials, simple and quick preparation method, green and environment-friendly synthesized carbon dots, no pollution, high fluorescence intensity and good corrosion inhibition performance. The invention not only enriches the types of fluorescent tracers, but also widens the application field of carbon dots and provides a new direction for the development of the fluorescent tracers.
Drawings
FIG. 1 is a graph showing fluorescence excitation and emission spectra of the carbon dot fluorescent tracer prepared in example 4 at a concentration of 12 mg/L;
FIG. 2 is a fluorescence emission spectrum of the carbon dot fluorescent tracer prepared in example 4 at different concentrations;
FIG. 3 is a graph showing the linear relationship between the concentration of the fluorescent tracer at carbon spots and the fluorescence intensity obtained in example 4;
FIG. 4 shows the concentration of 20mg/L NaClO (effective content 10% in Cl) in the carbon dot fluorescent tracer prepared in example 4, example 5, example 6 and example 7-Meter) plot of fluorescence intensity versus time;
FIG. 5 shows fluorescence intensities of the carbon dot fluorescent tracer prepared in example 4 at different pH values;
FIG. 6 is a graph of the corrosion inhibition efficiency of the carbon dot fluorescent tracer prepared in example 4 at different concentrations.
Detailed Description
The present invention will be further described with reference to the following examples.
Aiming at the defects of high price, complex preparation process and poor environmental protection performance of the existing fluorescent tracer, the invention provides a preparation method and application of a carbon dot fluorescent tracer.
Example 1
Weighing 0.210g of citric acid and 0.680g of monopotassium phosphate in a mortar, uniformly mixing and grinding the citric acid and the monopotassium phosphate into powder, transferring the ground raw materials into a crucible, heating the crucible at 230 ℃ for 8 hours, cooling the mixture to room temperature, adding 40mL of ultrapure water into the product, stirring and dissolving the mixture, carrying out reduced pressure suction filtration on the obtained solution to remove impurities, and finally dialyzing and purifying the solution in a dialysis bag with molecular weight cutoff of 500 for 48 hours to obtain the carbon dot fluorescent tracer.
Diluting the carbon dot fluorescent tracer prepared in the step, preparing a 20mg/L solution, and measuring the fluorescence intensity of the solution. The excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the optimal emission wavelength is 416nm under the optimal excitation wavelength of 362nm, and the fluorescence intensity is 1048.
Example 2
Weighing 0.210g of citric acid and 0.871g of dipotassium hydrogen phosphate into a mortar, uniformly mixing and grinding the mixture into powder, transferring the ground raw materials into a crucible, heating the crucible at the high temperature of 250 ℃ for 12 hours, cooling the mixture to room temperature, adding 50mL of ultrapure water into the product, stirring and dissolving the mixture, carrying out reduced pressure suction filtration on the obtained solution to remove impurities, and finally dialyzing and purifying the solution in a dialysis bag with the molecular weight cutoff of 500 for 48 hours to obtain the carbon dot fluorescent tracer.
Diluting the carbon dot fluorescent tracer prepared in the step, preparing a 20mg/L solution, and measuring the fluorescence intensity of the solution. The excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the optimal emission wavelength is 410nm under the optimal excitation wavelength of 362nm, and the fluorescence intensity is 2641.
Example 3
Weighing 0.210g of citric acid and 0.575g of ammonium dihydrogen phosphate into a mortar, uniformly mixing and grinding the mixture into powder, transferring the ground raw materials into a crucible, heating the crucible at a high temperature of 200 ℃ for 5 hours, cooling the mixture to room temperature, adding 10mL of ultrapure water into the product, stirring and dissolving the mixture, decompressing and filtering the obtained solution to remove impurities, and finally dialyzing and purifying the solution in a dialysis bag with molecular weight cutoff of 500 for 48 hours to obtain the carbon dot fluorescent tracer.
Diluting the carbon dot fluorescent tracer prepared in the step, preparing a 20mg/L solution, and measuring the fluorescence intensity of the solution. The excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the optimal emission wavelength is 430nm under the optimal excitation wavelength of 360nm, and the fluorescence intensity is 6890.
Example 4
Weighing 0.210g of citric acid and 0.660g of diammonium hydrogen phosphate in a mortar, uniformly mixing and grinding the citric acid and the diammonium hydrogen phosphate into powder, transferring the ground raw materials into a crucible, heating the crucible at a high temperature of 180 ℃ for 1 hour, cooling the mixture to room temperature, adding 15mL of ultrapure water into the product, stirring and dissolving the ultrapure water, carrying out vacuum filtration on the obtained solution to remove impurities, and finally dialyzing and purifying the solution in a dialysis bag with molecular weight cutoff of 500 for 48 hours to obtain the carbon point fluorescent tracer, wherein the solid content of the carbon point fluorescent tracer is 4.136%.
Diluting the carbon dot fluorescent tracer prepared in the step, preparing a 20mg/L solution, and measuring the fluorescence intensity of the solution. The excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the optimal emission wavelength is 444nm under the optimal excitation wavelength of 362nm, and the fluorescence intensity is 8203.
The fluorescence excitation spectrogram and the fluorescence emission spectrogram of the prepared carbon dot fluorescent tracer are tested, the test concentration is 12mg/L, the excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the result is shown in figure 1, and the graph shows that the fluorescence excitation spectrum and the emission spectrum of the prepared carbon dot fluorescent tracer have good mirror symmetry relationship, so that the prepared carbon dot fluorescent tracer has excellent fluorescence performance. Fluorescence spectrograms of the fluorescent material at different concentrations (the concentrations are respectively 2, 4, 6, 8, 10 and 12mg/L) are simultaneously tested, the measured results are shown in figure 2 under the condition that the excitation wavelength is 362nm, the measured fluorescence intensities are respectively 883, 1755, 2621, 3398, 4205 and 4993, and the results are shown in figure 3 after linear fitting is carried out on the fluorescence intensities and the concentrations. From fig. 3, the fluorescence intensity of the carbon dot fluorescent tracer increases with the increase of the concentration, and the two are in an excellent linear relationship, and the linear equation of the fluorescence intensity y and the concentration x of the carbon dot fluorescent tracer is calculated to be that y is 409.7x +107.5, and the linear correlation coefficient R is2Is 0.999, can meet the precision requirement of fluorescent tracing.
Example 5
Weighing 0.380g of citric acid and 0.550g of diammonium hydrogen phosphate in a mortar, uniformly mixing and grinding the citric acid and the diammonium hydrogen phosphate into powder, transferring the ground raw materials into a crucible, heating the crucible at a high temperature of 180 ℃ for 1 hour, cooling the mixture to room temperature, adding 15mL of ultrapure water into the product, stirring and dissolving the ultrapure water, carrying out vacuum filtration on the obtained solution to remove impurities, and finally dialyzing and purifying the solution in a dialysis bag with molecular weight cutoff of 1000 for 48 hours to obtain the carbon dot fluorescent tracer.
Diluting the carbon dot fluorescent tracer prepared in the step, preparing a 20mg/L solution, and measuring the fluorescence intensity of the solution. The excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the optimal emission wavelength is 441nm under the optimal excitation wavelength of 359nm, and the fluorescence intensity is 1765.
Example 6
Weighing 0.590g of citric acid and 0.420g of diammonium hydrogen phosphate in a mortar, uniformly mixing and grinding the citric acid and the diammonium hydrogen phosphate into powder, transferring the ground raw materials into a crucible, heating the crucible at a high temperature of 180 ℃ for 1h, cooling the mixture to room temperature, adding 20mL of ultrapure water into the product, stirring and dissolving the ultrapure water, carrying out vacuum filtration on the obtained solution to remove impurities, and finally dialyzing and purifying the solution in a dialysis bag with molecular weight cutoff of 2000 for 48h to obtain the carbon dot fluorescent tracer.
Diluting the carbon dot fluorescent tracer prepared in the step, preparing a 20mg/L solution, and measuring the fluorescence intensity of the solution. The excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the optimal emission wavelength is 423nm under the optimal excitation wavelength of 356nm, and the fluorescence intensity is 1690.
Example 7
Weighing 0.800g of citric acid and 0.240g of diammonium hydrogen phosphate in a mortar, uniformly mixing and grinding the citric acid and the diammonium hydrogen phosphate into powder, transferring the ground raw materials into a crucible, heating the crucible at a high temperature of 180 ℃ for 1h, cooling the mixture to room temperature, adding 20mL of ultrapure water into the product, stirring and dissolving the ultrapure water, carrying out vacuum filtration on the obtained solution to remove impurities, and finally dialyzing and purifying the solution in a dialysis bag with molecular weight cutoff of 3500 for 48h to obtain the carbon dot fluorescent tracer.
Diluting the carbon dot fluorescent tracer prepared in the step, preparing a 20mg/L solution, and measuring the fluorescence intensity of the solution. The excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the optimal emission wavelength is 424nm under the optimal excitation wavelength of 349nm, and the fluorescence intensity is 1311.
Example 8
Weighing 0.590g of citric acid and 0.420g of diammonium hydrogen phosphate in a mortar, uniformly mixing and grinding the mixture into powder, transferring the ground raw materials into a crucible, heating the crucible at a high temperature of 180 ℃ for 0.5h, cooling the mixture to room temperature, adding 20mL of ultrapure water into the product, stirring and dissolving the ultrapure water, carrying out vacuum filtration on the obtained solution to remove impurities, and finally dialyzing and purifying the solution in a dialysis bag with molecular weight cutoff of 2000 for 48h to obtain the carbon dot fluorescent tracer.
Diluting the carbon dot fluorescent tracer prepared in the step, preparing a 20mg/L solution, and measuring the fluorescence intensity of the solution. The excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the optimal emission wavelength is 423nm under the optimal excitation wavelength of 356nm, and the fluorescence intensity is 1230.
Example 9
Weighing 0.210g of citric acid and 0.660g of diammonium hydrogen phosphate in a mortar, uniformly mixing and grinding the citric acid and the diammonium hydrogen phosphate into powder, transferring the ground raw materials into a crucible, heating the crucible at a high temperature of 220 ℃ for 1 hour, cooling the mixture to room temperature, adding 15mL of ultrapure water into the product, stirring and dissolving the ultrapure water, carrying out vacuum filtration on the obtained solution to remove impurities, and finally dialyzing and purifying the solution in a dialysis bag with molecular weight cutoff of 500 for 48 hours to obtain the carbon dot fluorescent tracer.
Diluting the carbon dot fluorescent tracer prepared in the step, preparing a 20mg/L solution, and measuring the fluorescence intensity of the solution. The excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the optimal emission wavelength is 444nm under the optimal excitation wavelength of 362nm, and the fluorescence intensity is 2478.
Example 10
Weighing 0.210g of citric acid and 0.660g of diammonium hydrogen phosphate in a mortar, uniformly mixing and grinding the citric acid and the diammonium hydrogen phosphate into powder, transferring the ground raw materials into a crucible, heating the crucible at a high temperature of 120 ℃ for 24 hours, cooling the mixture to room temperature, adding 15mL of ultrapure water into the product, stirring and dissolving the ultrapure water, carrying out vacuum filtration on the obtained solution to remove impurities, and finally dialyzing and purifying the solution in a dialysis bag with molecular weight cutoff of 500 for 48 hours to obtain the carbon dot fluorescent tracer.
Diluting the carbon dot fluorescent tracer prepared in the step, preparing a 20mg/L solution, and measuring the fluorescence intensity of the solution. The excitation bandwidth and the emission bandwidth are both 10nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, the optimal emission wavelength is 444nm under the optimal excitation wavelength of 362nm, and the fluorescence intensity is 2754.
Example 11
A certain amount of sodium hypochlorite can be added into industrial circulating water cooling water for sterilization and microorganism growth control, and the addition of the sodium hypochlorite generally has great influence on the performance of a fluorescent tracer in the water. Therefore, the present inventors examined the effect of sodium hypochlorite on the fluorescence properties of the carbon dot fluorescent tracers prepared in examples 4, 5, 6 and 7. Sodium hypochlorite (10% active content, in Cl)-Meter) concentration of 20mg/L, solution pH of 8.5, and fluorescence intensity of each sample with time was measured at an excitation wavelength of 362nm and an emission wavelength of 444nm, and the results are shown in fig. 4. As can be seen from the figure, the fluorescence intensity of each sample is still stable with the time increase under the condition of 2mg/L of sodium hypochlorite, and the invention shows that the prepared carbon dot fluorescent tracer has good stability to the sodium hypochlorite.
Example 12
The pH of industrial circulating water is generally 6 to 9, and therefore, the invention explores the influence of the pH value of 6 to 11 on the fluorescence intensity of the carbon dot fluorescent tracer prepared in example 4. The pH of the solution was adjusted with 1mol/L NaOH, and the fluorescence intensity of each sample was measured at an excitation wavelength of 362nm and an emission wavelength of 444nm, and the results are shown in FIG. 5. As can be seen from the figure, the fluorescence intensity is hardly affected when the pH value is 6-10, and the fluorescence intensity changes more obviously and decreases slightly when the pH value is higher than 10. Therefore, the fluorescence intensity of the carbon dot fluorescent tracer prepared by the invention is hardly influenced in the pH value condition of industrial circulating water.
Example 13
The invention adopts national standard GB/T18175-2014 'test for water treatment agent corrosion inhibition performance-rotary hanging sheet method' to test the corrosion inhibition performance of the carbon dot fluorescent tracer prepared in the example 4 to Q235 carbon steel in 3 wt% NaCl solution. The test temperature was 25 ℃ and the time was 72h, and the results are shown in FIG. 6. From the figure, it can be seen that the corrosion inhibition rate is continuously increased along with the increase of the concentration of the carbon dot fluorescent tracer, and when the concentration is 200mg/L, the corrosion inhibition rate can reach 61.3 percent, which indicates that the prepared carbon dot fluorescent tracer has a certain corrosion inhibition effect.
The method is simple, the synthetic raw materials are cheap and easy to obtain, and the synthesized carbon dots have high fluorescence intensity and stability, so that the defects of high price, complex preparation and poor environmental protection of the conventional fluorescent tracer are overcome. Meanwhile, the carbon dots synthesized by the method also have certain corrosion inhibition performance, can protect metals from being corroded while detecting the medicament in the water body, has multiple functions, and greatly reduces the use cost of the medicament.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and is not intended to limit the invention to the particular forms disclosed. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A preparation method of a carbon dot fluorescent tracer is characterized by comprising the following steps: mixing citric acid and phosphate, grinding into powder, placing the powder raw material in a container for high-temperature heating reaction, cooling to room temperature after the reaction is finished, adding ultrapure water into the container, stirring for dissolving, removing insoluble impurities through suction filtration, and finally performing dialysis purification by using a dialysis bag to obtain the carbon dot fluorescent tracer.
2. The method for preparing a carbon dot fluorescent tracer according to claim 1, wherein: the phosphate is selected from one or the combination of more than two of diammonium hydrogen phosphate, dipotassium hydrogen phosphate, ammonium dihydrogen phosphate or potassium dihydrogen phosphate.
3. The method for preparing a carbon dot fluorescent tracer according to claim 2, wherein: the phosphate is diammonium hydrogen phosphate.
4. The method for preparing a carbon dot fluorescent tracer according to claim 1, wherein: the mass ratio of the citric acid to the phosphate is 1: (0.3-4.5).
5. The method for preparing a carbon dot fluorescent tracer according to claim 1, wherein: the mass ratio of the citric acid to the ultrapure water is 1: (25-240).
6. The method for preparing a carbon dot fluorescent tracer according to claim 1, wherein: the container for high-temperature heating reaction is a crucible with a cover.
7. The method for preparing a carbon dot fluorescent tracer according to claim 1, wherein: the heating temperature of the high-temperature heating reaction is 120-250 ℃, and the reaction time is 0.5-24 h.
8. The method for preparing a carbon dot fluorescent tracer according to claim 1, wherein: the dialysis bag is a dialysis bag with the molecular weight cutoff of 500-3500.
9. A carbon dot fluorescent tracer prepared by the method of any one of claims 1 to 8.
10. Use of the carbon dot fluorescent tracer according to claim 9 in circulating cooling water.
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