CN111044495A - Carbon quantum dot-based seawater corrosion and scale inhibitor and fluorescent tracing detection method thereof - Google Patents
Carbon quantum dot-based seawater corrosion and scale inhibitor and fluorescent tracing detection method thereof Download PDFInfo
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- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 132
- 230000007797 corrosion Effects 0.000 title claims abstract description 126
- 238000005260 corrosion Methods 0.000 title claims abstract description 126
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 59
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000012360 testing method Methods 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 27
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- 239000013505 freshwater Substances 0.000 claims abstract description 8
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- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 238000012417 linear regression Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000011852 carbon nanoparticle Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001408 amides Chemical group 0.000 description 1
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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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
Abstract
The invention relates to the technical field of seawater treatment, in particular to a carbon quantum dot-based fluorescent probe type seawater corrosion and scale inhibitor and a fluorescent tracing detection method thereof. The corrosion and scale inhibitor is prepared by mixing a carbon quantum dot serving as a fluorescent tracer and a basic seawater corrosion and scale inhibitor. The fluorescent tracing detection method comprises the following steps: testing the fluorescence intensity of a seawater sample as a substrate; adding a fluorescent probe type seawater corrosion and scale inhibitor with known concentration into a seawater sample, and testing the fluorescence intensity of the water sample under each concentration; deducting the substrate and then drawing a working curve of fluorescence intensity and concentration; adding a fluorescent probe type seawater corrosion and scale inhibitor into a seawater sample, and testing the fluorescence intensity of the water sample containing the fluorescent probe type seawater corrosion and scale inhibitor; after the fluorescence intensity is deducted from the substrate, the concentration of the seawater corrosion and scale inhibitor is measured according to the working curve, and the method is simple, short in detection period, high in accuracy, easy to realize and simultaneously suitable for the field of seawater and fresh water.
Description
Technical Field
The invention relates to the technical field of seawater treatment, in particular to a carbon quantum dot-based fluorescent probe type seawater corrosion and scale inhibitor and a fluorescent tracing detection method thereof.
Background
The quality of the seawater water treatment effect is directly related to the addition amount of the medicament, and the monitoring of the medicament content in the system has important significance. In order to achieve the desired water treatment, reliable methods for monitoring and controlling the concentration of the agent are needed. However, the method of adding the medicament according to the flow of the seawater generally adopted at present has the problems of incapability of visually reflecting the concentration of the medicament in the system, untimely response to system fluctuation, low accuracy and the like. The fluorescent tracing type water treatment agent can well solve the problem, has the advantages of simple and rapid test method, high accuracy and the like, and can form an on-line monitoring and automatic dosing control technology. However, most of the existing fluorescent tracers contain condensed rings in the structure, and have the limitations of certain toxicity, difficult degradation, high price and the like. Meanwhile, the seawater has complex composition, high salt content and certain fluorescence characteristic. Therefore, few research reports on the fluorescent tracing monitoring technology applicable to the seawater system exist.
The carbon quantum dot is a carbon nano particle with a shell-core structure, has an obvious quantum effect, and is one of environment-friendly fluorescent materials. The carbon quantum dots suitable for the seawater environment have stable fluorescence characteristics in a seawater medium, do not react with a medicament, and have incomparable advantages of bleaching resistance, low toxicity, low cost, good biocompatibility and the like. Therefore, the invention provides a carbon quantum dot as a fluorescent tracing material of the seawater corrosion and scale inhibitor, and discloses a fluorescent tracing detection method of the seawater corrosion and scale inhibitor based on the carbon quantum dot. The method can realize the monitoring and control of the concentration of the medicament.
Disclosure of Invention
The invention solves the technical problem that the concentration of a seawater corrosion and scale inhibitor is monitored and controlled according to the requirement of safe operation of seawater utilization engineering, and provides a fluorescent probe type seawater corrosion and scale inhibitor based on carbon quantum dots and a fluorescent tracing detection method aiming at the limitation of the existing fluorescent tracing material. The method adopts carbon quantum dots as a fluorescent tracer, and mixes the fluorescent tracer with a basic seawater corrosion and scale inhibitor to obtain the fluorescent probe type seawater corrosion and scale inhibitor based on the carbon quantum dots.
On the other hand, the invention also provides a fluorescent tracing detection method of the fluorescent probe type water treatment medicament, which comprises the following steps:
(1) uniformly mixing the carbon quantum dots and the seawater corrosion and scale inhibitor;
(2) testing the fluorescence intensity of a seawater sample as a substrate;
(3) adding a fluorescence probe type seawater corrosion and scale inhibitor with known concentration into a seawater sample, and testing the fluorescence intensity of the water sample;
(4) deducting the fluorescence intensity measured in the step (3) from the substrate, and then drawing a working curve of the fluorescence intensity and the concentration of the fluorescence probe type seawater corrosion and scale inhibitor;
(5) testing the fluorescence intensity of a water sample to be tested containing the fluorescence probe type seawater corrosion and scale inhibitor;
(6) and (5) subtracting the substrate from the fluorescence intensity measured in the step (5), and calculating the concentration of the seawater corrosion and scale inhibitor according to the working curve.
Specifically, in order to solve the above technical problems, the present invention provides the following technical solutions:
a fluorescent probe type seawater corrosion and scale inhibitor based on carbon quantum dots is disclosed, wherein the scale inhibitor comprises the carbon quantum dots serving as a fluorescent tracer and a basic seawater corrosion and scale inhibitor, and the mass ratio of the carbon quantum dots to the basic seawater corrosion and scale inhibitor is (1-100):1000, parts by weight; preferably (1-5): 1000.
preferably, the scale inhibitor is one or more selected from the group consisting of (poly) carboxylic acid and derivatives thereof, corrosion and scale inhibitor of (poly) epoxy succinic acid and derivatives thereof, corrosion and scale inhibitor of (poly) maleic acid and derivatives thereof, corrosion and scale inhibitor of (poly) itaconic acid and derivatives thereof, phosphorus-containing corrosion and scale inhibitor, and complex corrosion and scale inhibitor, preferably (poly) carboxylic acid and derivatives thereof.
Preferably, for the scale inhibitor, the carbon quantum dot structure is core-shell structure carbon nanoparticles, and the particle size is preferably less than 10nm, and more preferably 0.5nm to 3 nm.
A fluorescent tracing detection method of a fluorescent probe type seawater corrosion and scale inhibitor based on carbon quantum dots is characterized by comprising the following steps:
(1) uniformly mixing the carbon quantum dots and the basic seawater corrosion and scale inhibitor to obtain the fluorescent probe type seawater corrosion and scale inhibitor;
(2) testing the fluorescence intensity A of a seawater sample as a substrate;
(3) adding the corrosion and scale inhibitor obtained in the step (1) with different concentrations into a seawater sample, and testing the fluorescence intensity of the water sample under each concentration;
(4) deducting the fluorescence intensity of the water sample with each concentration measured in the step (3) from the substrate in the step (2), and then drawing a working curve and/or a linear regression equation of the fluorescence intensity and the concentration of the fluorescence probe type seawater corrosion and scale inhibitor;
(5) testing the fluorescence intensity C of a water sample to be tested containing the fluorescence probe type seawater corrosion and scale inhibitor;
(6) and (5) after the fluorescence intensity measured in the step (5) is deducted from the substrate, calculating the concentration of the fluorescence probe type seawater corrosion and scale inhibitor according to a working curve and/or a linear regression equation.
Preferably, for the detection method, wherein the test water sample used is selected from a seawater water sample or a freshwater water sample.
Preferably, for the detection method, the relationship between the carbon quantum dot fluorescence signal B and the seawater autofluorescence signal a is as follows: b > A.
Preferably, for the detection method, when the concentration of the fluorescent probe-type seawater corrosion and scale inhibitor is determined in step (6), the fluorescence intensity a of the seawater substrate is subtracted from the measured fluorescence intensity C, i.e., the actual fluorescence intensity is C-a.
Preferably, for the detection method, the fluorescence probe type seawater corrosion and scale inhibitor has the characteristic that the fluorescence intensity is in a linear relation with the concentration, R >0.9, and preferably R > 0.99.
The fluorescent probe type seawater corrosion and scale inhibitor or the fluorescent tracing detection method in any section can be applied to the field of seawater or fresh water treatment.
Preferably, for the application of the fluorescent probe type seawater corrosion and scale inhibitor, the concentration of the scale inhibitor is 1-200mg/L, preferably 1-100mg/L, and more preferably 1-50 mg/L.
The beneficial effects of the invention include:
(1) the detection method provided by the invention is simple, short in detection period, high in accuracy and easy to realize;
(2) the carbon quantum dots adopted by the fluorescent probe type corrosion and scale inhibitor provided by the invention do not contain condensed rings, so that the fluorescent probe type corrosion and scale inhibitor is green and environment-friendly and has low cost;
(3) the carbon quantum dots adopted by the fluorescent probe type corrosion and scale inhibitor provided by the invention are slightly influenced by seawater and a medicament, and meanwhile, the fluorescent signals of the carbon quantum dots are obviously different from the fluorescent signals of the seawater;
(4) the fluorescence probe type corrosion and scale inhibitor and the detection method thereof overcome the difficulties that a seawater system has high salinity, complex components, fluorescence characteristics and the like, and can be applied to the fluorescence tracing monitoring of the seawater corrosion and scale inhibitor;
(5) the fluorescent probe type corrosion and scale inhibitor and the detection method thereof provided by the invention can also be applied to the fluorescent tracing detection of fresh water treatment agents, and have good economic and social benefits.
Drawings
FIG. 1 is a working curve of the fluorescent probe type seawater corrosion and scale inhibitor in seawater in example 1, and the regression equation is as follows: y is 16.47x-2.579 and the linear relationship of the operating curve is fit to R0.9999.
Fig. 2 is a working curve of the fluorescent probe-type seawater corrosion and scale inhibitor of example 2 in 2-fold concentrated seawater, where the regression equation is that Y is 3.974x +0.98, and the linear relationship of the working curve is that R is 0.9999.
Fig. 3 is a working curve of the fluorescent probe-type seawater corrosion and scale inhibitor of example 3 in tap water, where the regression equation is 3.845x +1.659, and the linear relationship of the working curve is 0.9999.
Fig. 4 is a working curve of the fluorescent probe-type corrosion and scale inhibitor of example 4 in tap water, where the regression equation is 2.375x +4.838, and the linear relationship of the working curve is 0.9989.
Fig. 5 is a working curve of the fluorescent probe-type seawater corrosion and scale inhibitor of example 5 in seawater, where the regression equation is 7.168x +10.76, and the linear relationship of the working curve is R0.9999.
Detailed Description
The invention provides a fluorescent probe type seawater corrosion and scale inhibitor based on carbon quantum dots in order to overcome the defects of high cost, certain toxicity, difficult degradation and the like of the existing fluorescent tracer type water treatment agent, wherein the environment-friendly carbon quantum dots are used as the fluorescent tracer and are mixed with a basic seawater corrosion and scale inhibitor to prepare the fluorescent probe type seawater corrosion and scale inhibitor; wherein the mass ratio of the carbon quantum dots to the basic seawater corrosion and scale inhibitor is (1-100): 1000.
in a preferred embodiment of the invention, the mass ratio of the carbon quantum dots to the basic seawater corrosion and scale inhibitor is (1-5): 1000.
in a preferred embodiment of the invention, the commercial sources and the commercial models of the raw materials used are respectively:
(1) the basic seawater corrosion and scale inhibitor (the model is SW203 and SW203A) and the carbon quantum dots (FT101, the particle size is 0.5-3nm) are all products produced by Tianjin seawater desalination and comprehensive utilization research institute of the department of natural resources, and the Zhonghai water treatment science and technology Limited company in Tianjin city;
(2) wherein, the basic seawater corrosion and scale inhibitor (model: HEDP) is purchased from Shandongtai and water treatment science and technology GmbH.
(3) The types of the seawater slow-release scale inhibitor with different types are respectively as follows:
SW203 is a multi-component composite scale inhibition and dispersion agent, takes a copolymer as a main component, contains a plurality of functional groups such as carboxylic acid, amide, hydroxyl, sulfonic acid and the like, and belongs to corrosion and scale inhibitors of (poly) carboxylic acid and derivatives thereof;
SW203A is a high-efficiency, non-phosphorus, environment-friendly composite scale-inhibiting dispersant, belonging to corrosion and scale inhibitors of (poly) epoxy succinic acid and derivatives thereof;
HEDP belongs to a phosphorus-containing corrosion and scale inhibitor.
In a preferred embodiment of the invention, the concentration of the fluorescent probe type seawater corrosion and scale inhibitor is used in the range of 1-200 mg/L.
In a preferred embodiment of the invention, the concentration of the fluorescent probe type seawater corrosion and scale inhibitor is used in the range of 1-50 mg/L.
The invention also provides a tracing detection method of the fluorescent probe type seawater corrosion and scale inhibitor based on the carbon quantum dots, which comprises the following steps:
(1) uniformly mixing the carbon quantum dots and the seawater corrosion and scale inhibitor;
(2) testing the fluorescence intensity of a water sample as a substrate;
(3) adding a fluorescence probe type seawater corrosion and scale inhibitor with known concentration into a water sample, and testing the fluorescence intensity of the water sample;
(4) deducting the fluorescence intensity measured in the step (3) from the substrate, and then drawing a working curve of the fluorescence intensity and the concentration of the fluorescence probe type seawater corrosion and scale inhibitor;
(5) testing the fluorescence intensity of a water sample containing the fluorescence probe type seawater corrosion and scale inhibitor;
(6) and (5) subtracting the substrate from the fluorescence intensity measured in the step (5), and calculating the concentration of the seawater corrosion and scale inhibitor according to the working curve.
In a preferred embodiment of the invention, the source of the seawater sample is seawater which is taken out from Bohai sea and subjected to sedimentation pretreatment; the tap water sample is tap water from Tianjin city.
In a preferred embodiment of the present invention, the fluorescence intensity detection method comprises the following specific steps: a fluorescence characteristic test is carried out by using a Hitachi F-7000 fluorescence spectrophotometer under the conditions that the excitation wavelength is 343nm, the emission wavelength is 435nm and the scanning speed is 1200 nm/min.
The technical solution of the present invention will be further clearly and completely described by the following specific examples. It is apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without any inventive step, also belong to the scope of protection of the present invention.
Examples
Example 1
(1) Drawing a working curve
Adopting carbon quantum dots FT101 as a fluorescent tracer; preparing a fluorescent probe type seawater corrosion and scale inhibitor with SW203 seawater corrosion and scale inhibitor according to the mass ratio of 1 per thousand (0.02 g FT101 carbon quantum dots are added into 20g of SW203 seawater corrosion and scale inhibitor), testing the fluorescence intensity of a seawater sample under the condition that the excitation slit width and the emission slit width are both 5.0nm, and testing the fluorescence intensity of the water sample containing the fluorescent probe type seawater corrosion and scale inhibitor with different concentrations (1mg/L, 2mg/L, 5mg/L, 10mg/L, 15mg/L, 20mg/L and 25 mg/L); after deducting the substrate, drawing a working curve of the fluorescence intensity and the concentration of the fluorescence probe type seawater corrosion and scale inhibitor as follows: y is 16.47x-2.579, and the linear relationship of the working curve is fit to R is 0.9999 (as in fig. 1).
(2) Determining the concentration of the traditional Chinese medicine in the water sample according to the working curve:
a. firstly, preparing 10g/L aqueous solution of the fluorescence probe type seawater corrosion and scale inhibitor in the step (1);
b. taking 5 1000mL volumetric flasks, sequentially adding 0.1mL, 0.3mL, 0.5mL, 1.0mL and 2.0mL of the 10g/L fluorescence probe type seawater corrosion and scale inhibitor, respectively diluting the 10g/L fluorescence probe type seawater corrosion and scale inhibitor to a scale with a seawater sample, and shaking up to obtain solutions with actual concentrations of 1mg/L, 3mg/L, 5mg/L, 10mg/L and 20mg/L respectively; then, according to the detection method of the fluorescent probe type seawater corrosion and scale inhibitor based on the carbon quantum dots, the method comprises the following steps:
c. testing the fluorescence intensity of the water sample with each concentration in the step b;
d. after subtracting the substrate from the fluorescence intensity in the step c, respectively obtaining the fluorescence intensities of 14.7, 45.7,78.5,163.4 and 325.7, and determining the concentration corresponding to each fluorescence intensity through the working curve, wherein the concentration is respectively 1.05mg/L, 2.93mg/L, 4.92mg/L, 10.08mg/L and 19.93 mg/L;
and d, errors between the concentration measured in the step d and the actual concentration are less than 0.1mg/L, and the result of the fluorescent tracing detection method is proved to be accurate.
Example 2
(1) Drawing a working curve:
adopting carbon quantum dots FT101 as a fluorescent tracer, preparing a fluorescent probe type seawater corrosion and scale inhibitor (0.1 g of FT101 carbon quantum dots are added into 20g of SW203A seawater corrosion and scale inhibitor) with SW203A according to the mass ratio of 5 per thousand, testing the self fluorescence intensity of a 2-time seawater sample (2L of seawater is evaporated and concentrated to 1L at 40 ℃) under the condition that the excitation slit width and the emission slit width are both 2.5nm, and testing the fluorescence intensity of the water samples containing the fluorescent probe type seawater corrosion and scale inhibitor with different concentrations (1mg/L, 2mg/L, 5mg/L, 10mg/L, 15mg/L, 25mg/L and 50 mg/L); after deducting the substrate, a working curve Y of fluorescence intensity and concentration of the fluorescence probe type seawater corrosion and scale inhibitor is drawn as 3.974x +0.98, and a linear relation of the working curve is R as 0.9999 (as shown in fig. 2).
(2) Determining the concentration of the traditional Chinese medicine in the water sample according to the working curve:
a. firstly, preparing 1.0g/L aqueous solution of the fluorescence probe type seawater corrosion and scale inhibitor in the step (1);
b. taking 5 100mL volumetric flasks, sequentially adding 0.1mL, 0.5mL, 1.0mL, 1.5mL and 2.0mL of the fluorescent probe type seawater corrosion and scale inhibitor of 1.0g/L in the step a, diluting the concentrated seawater of 2 times to a scale respectively, shaking up, and respectively setting the actual concentrations to be 1mg/L, 5mg/L, 10mg/L, 15mg/L and 20 mg/L;
then, according to the detection method of the fluorescent probe type seawater corrosion and scale inhibitor based on the carbon quantum dots, the method comprises the following steps:
c. testing the fluorescence intensity of the water sample with each concentration in the step b;
d. after the fluorescence intensity in the step c is subtracted from the substrate, the fluorescence intensity is 5.11, 20.65, 40.40, 60.95 and 80.10 respectively; determining the concentration corresponding to each fluorescence intensity through a working curve, wherein the concentration is 1.04mg/L, 4.95mg/L, 9.92mg/L, 15.09mg/L and 19.91mg/L respectively;
and d, errors between the concentration measured in the step d and the actual concentration are less than 0.1mg/L, and the result of the fluorescent tracing detection method is proved to be accurate.
Example 3
(1) Drawing a working curve
Carbon quantum dots FT101 are used as fluorescent tracers, and HEDP (0.1 g of FT101 carbon quantum dots are added into 20g of HEDP seawater corrosion and scale inhibitor) is mixed with HEDP by a mass ratio of 5 per mill to prepare a fluorescent probe type water treatment agent. Under the condition that the widths of excitation slits and emission slits are both 2.5nm, the fluorescence intensity of tap water and the fluorescence intensity of water samples containing fluorescent probe type corrosion and scale inhibitors with different concentrations (1mg/L, 2mg/L, 5mg/L, 10mg/L, 15mg/L, 25mg/L, 50mg/L, 80mg/L and 100mg/L) are tested; after deducting the substrate, the working curve of the concentration of the fluorescent probe type corrosion and scale inhibitor and the fluorescence intensity in the tap water is plotted as Y being 3.845x +1.659, and the linear relation of the working curve is R being 0.9999 (as shown in fig. 3).
(2) Determining the concentration of the traditional Chinese medicine in the water sample according to the working curve:
a. firstly, preparing a 10g/L concentration solution (prepared by distilled water) of the fluorescence probe type seawater corrosion and scale inhibitor in the step (1);
b. taking 5 1000mL volumetric flasks, sequentially adding 0.1mL, 1.0mL, 5.0mL, 7.5mL and 10mL of the 10g/L fluorescent probe seawater corrosion and scale inhibitor in the step a, respectively diluting the 10g/L fluorescent probe seawater corrosion and scale inhibitor to scales by using a tap water sample, and shaking up the samples to obtain actual concentrations of 1mg/L, 10mg/L, 50mg/L, 75mg/L and 100 mg/L;
then, according to the detection method of the fluorescent probe type seawater corrosion and scale inhibitor based on the carbon quantum dots, the method comprises the following steps:
c. testing the fluorescence intensity of the water sample with each concentration in the step b;
d. after the fluorescence intensity in the step c is subtracted from the substrate, the fluorescence intensity is respectively 5.27, 39.92, 194.2, 289.7 and 385.8, and the concentration corresponding to each fluorescence intensity is determined by a working curve and respectively 0.94mg/L, 9.95mg/L, 50.08mg/L, 74.91mg/L and 99.91 mg/L;
and d, errors between the concentration measured in the step d and the actual concentration are less than 0.1mg/L, and the results prove that the fluorescent tracing detection method can be applied to fresh water treatment and is accurate.
Example 4
(1) Drawing a working curve
Carbon quantum dots FT101 are used as fluorescent tracers, and a fluorescent probe type water treatment agent is prepared by mixing SW203 with SW 100:1000 in a mass ratio (1 g of FT101 carbon quantum dots are added in 10g of SW203 seawater corrosion and scale inhibitor). Under the condition that the widths of excitation slits and emission slits are both 1nm, the fluorescence intensity of seawater and the fluorescence intensity of water samples containing fluorescent probe type corrosion and scale inhibitors (2.5mg/L, 5mg/L, 10mg/L, 25mg/L and 50mg/L) with different concentrations are tested; after deducting the substrate, the working curve of the concentration of the fluorescent probe type corrosion and scale inhibitor and the fluorescence intensity in the seawater is plotted as Y2.375 x +4.838, and the linear relation of the working curve is R0.9989 (as shown in fig. 4).
(2) Determining the concentration of the traditional Chinese medicine in the water sample according to the working curve:
a. firstly, preparing a 10g/L concentration solution (prepared by distilled water) of the fluorescence probe type seawater corrosion and scale inhibitor in the step (1);
b. taking 5 1000mL volumetric flasks, sequentially adding 1.0mL, 1.5mL, 2.0mL, 3.0mL and 5.0mL of the 10g/L fluorescent probe seawater corrosion and scale inhibitor in the step a, diluting the seawater samples to scales respectively, shaking up, and respectively setting the actual concentrations to 10mg/L, 15mg/L, 20mg/L, 30mg/L and 50 mg/L;
then, according to the detection method of the fluorescent probe type seawater corrosion and scale inhibitor based on the carbon quantum dots, the method comprises the following steps:
c. testing the fluorescence intensity of the water sample with each concentration in the step b;
d. after subtracting the substrate from the fluorescence intensity in the step c, the fluorescence intensity is 29.05, 40.25, 51.65, 76.95 and 121.3 respectively, and the concentration corresponding to each fluorescence intensity is determined by the working curve to be 10.19mg/L, 14.91mg/L, 19.71mg/L, 30.36mg/L and 49.04mg/L respectively;
and d, errors between the concentration measured in the step d and the actual concentration are less than 1mg/L (< 2%), and the result of the fluorescent tracing detection method is accurate.
Example 5
(1) Drawing a working curve
Carbon quantum dot FT101 is used as a fluorescent tracer, and the mass ratio is 10: 1000 and SW203 were made into fluorescent probe type water treatment agent (10 g SW203 seawater corrosion and scale inhibitor added with 0.1g FT101 carbon quantum dots). Under the condition that the widths of excitation slits and emission slits are both 2.5nm, the fluorescence intensity of tap water and the fluorescence intensity of water samples containing fluorescent probe type corrosion and scale inhibitors with different concentrations (1mg/L, 5mg/L, 10mg/L, 25mg/L, 50mg/L, 100mg/L and 250mg/L) are tested; after deducting the substrate, the working curve of the concentration of the fluorescent probe-type corrosion and scale inhibitor and the fluorescence intensity in the tap water is plotted as Y being 7.168x +10.76, and the linear relation of the working curve is R being 0.9999 (as shown in fig. 5).
(2) Determining the concentration of the traditional Chinese medicine in the water sample according to the working curve:
a. firstly, preparing a 10g/L concentration solution (prepared by distilled water) of the fluorescence probe type seawater corrosion and scale inhibitor in the step (1);
b. taking 5 1000mL volumetric flasks, sequentially adding 2.0mL, 5.0mL, 7.5mL and 20mL of the 10g/L fluorescent probe seawater corrosion and scale inhibitor in the step a, respectively diluting the 10g/L fluorescent probe seawater corrosion and scale inhibitor to scales by using a tap water sample, and shaking up to obtain actual concentrations of 20mg/L, 50mg/L, 75mg/L, 150mg/L and 200 mg/L;
then, according to the detection method of the fluorescent probe type seawater corrosion and scale inhibitor based on the carbon quantum dots, the method comprises the following steps:
c. testing the fluorescence intensity of the water sample with each concentration in the step b;
d. after subtracting the substrate from the fluorescence intensity in the step c, the fluorescence intensity is 153.7, 373.8, 545.2, 1079.8 and 1438.6 respectively, and the concentration corresponding to each fluorescence intensity is determined by a working curve to be 19.94mg/L, 50.65mg/L, 74.56mg/L, 149.14mg/L and 199.19mg/L respectively;
and d, errors between the concentration measured in the step d and the actual concentration are less than 1mg/L (< 1%), and the result of the fluorescent tracing detection method is accurate.
From the above examples it can be seen that:
(1) the fluorescent probe type seawater corrosion and scale inhibitor based on the carbon quantum dots has a good linear relation between the concentration and the fluorescence intensity when a working curve is drawn, and the linear relation can reach 0.999;
(2) and can obtain the accurate test result under the condition that the addition amount of the carbon quantum dot of the invention is 1-5 per mill, namely can distinguish the fluorescence intensity of the carbon quantum dot and sea water itself under this addition amount, then when the addition amount of the carbon quantum dot is greater than this range ((1-100):1000), distinguish the fluorescence intensity of the two more easily, can also reach the good fluorescent tracing effect, the experimenter can adjust the addition amount of the carbon quantum dot according to the actual experiment, in order to reach the best fluorescent tracing effect;
(3) in addition, when the concentration of the medicament in a water sample is measured, the error between the measured concentration and the actual adding concentration under the optimal condition is less than 0.1mg/L, the error under other conditions is less than 1mg/L (less than 2%), and the measurement result is accurate, so that the fluorescent probe type seawater corrosion and scale inhibitor based on the carbon quantum dots and the fluorescent tracing detection method have good application effects in the field of seawater and fresh water treatment.
Claims (10)
1. A fluorescent probe type seawater corrosion and scale inhibitor based on carbon quantum dots is characterized by comprising the carbon quantum dots serving as a fluorescent tracer and a basic seawater corrosion and scale inhibitor, wherein the mass ratio of the carbon quantum dots to the basic seawater corrosion and scale inhibitor is (1-100):1000, parts by weight; preferably (1-5): 1000.
2. the seawater corrosion and scale inhibitor according to claim 1, wherein the basic seawater corrosion and scale inhibitor is one or more selected from (poly) carboxylic acid and derivatives thereof, a (poly) epoxy succinic acid and derivatives thereof, a (poly) maleic acid and derivatives thereof, a (poly) itaconic acid and derivatives thereof, a phosphorus-containing corrosion and scale inhibitor, and a complex type corrosion and scale inhibitor, and preferably a (poly) carboxylic acid and derivatives thereof.
3. The seawater corrosion and scale inhibitor according to claim 1 or 2, wherein the carbon quantum dot structure is a core-shell structure carbon nanoparticle, preferably the particle size of the carbon quantum dot is less than 10nm, and more preferably 0.5nm-3 nm.
4. The fluorescent tracing detection method of the carbon quantum dot-based fluorescent probe type seawater corrosion and scale inhibitor is characterized by comprising the following steps of:
(1) uniformly mixing the carbon quantum dots and the basic seawater corrosion and scale inhibitor to obtain the fluorescent probe type seawater corrosion and scale inhibitor;
(2) testing the fluorescence intensity A of a seawater sample as a substrate;
(3) adding the corrosion and scale inhibitor obtained in the step (1) with different concentrations into a seawater sample, and testing the fluorescence intensity of the water sample under each concentration;
(4) deducting the fluorescence intensity of the water sample with each concentration measured in the step (3) from the substrate in the step (2), and then drawing a working curve and/or a linear regression equation of the fluorescence intensity and the concentration of the fluorescence probe type seawater corrosion and scale inhibitor;
(5) testing the fluorescence intensity C of a water sample to be tested containing the fluorescence probe type seawater corrosion and scale inhibitor;
(6) and (5) after the fluorescence intensity measured in the step (5) is deducted from the substrate, calculating the concentration of the fluorescence probe type seawater corrosion and scale inhibitor according to a working curve and/or a linear regression equation.
5. The detection method according to claim 4, wherein the test water sample is selected from a seawater sample or a freshwater sample.
6. The detection method according to claim 4 or 5, wherein the relation between the carbon quantum dot fluorescence signal B and the seawater autofluorescence signal A is as follows: b > A.
7. The detection method according to any one of claims 4 to 6, wherein, when the concentration of the fluorescent probe-type seawater corrosion and scale inhibitor is measured in step (6), the measured fluorescence intensity C is subtracted from the fluorescence intensity A of the seawater substrate, i.e. the actual fluorescence intensity is C-A.
8. The detection method according to any one of claims 4 to 7, wherein the fluorescent probe-type seawater corrosion and scale inhibitor has a characteristic R >0.9 that the fluorescence intensity is in a linear relationship with the concentration; preferably R > 0.99.
9. The fluorescent probe-type seawater corrosion and scale inhibitor as defined in any one of claims 1 to 3 or the fluorescent tracing detection method as defined in any one of claims 4 to 8, which is applied in the field of seawater or fresh water treatment.
10. The application of the fluorescent probe-type seawater corrosion and scale inhibitor according to claim 9, wherein the concentration of the scale inhibitor is 1-200mg/L, preferably 1-100mg/L, and more preferably 1-50 mg/L.
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