CN108088820B - Method for quantitatively detecting hydroxyl free radicals by using laser flash photolysis technology - Google Patents
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Abstract
A method for quantitatively detecting hydroxyl free radicals by utilizing a laser flash photolysis technology is characterized by measuring the characteristic transient emission spectrum of a 2-hydroxy terephthalic acid standard solution with each concentration by utilizing a laser flash photolysis spectrometer to obtain the emission intensity at the maximum emission wavelength and drawing a standard curve of the corresponding relation between the concentration of the 2-hydroxy terephthalic acid standard solution and the emission intensity. And (3) taking terephthalic acid as a trapping agent, trapping hydroxyl radicals in a system to be detected, and generating a trapping product 2-hydroxy terephthalic acid. And under the excitation of specific laser wavelength, measuring the characteristic transient emission spectrum of the system to be measured containing hydroxyl free radicals added with excessive trapping agent terephthalic acid to obtain the concentration of the trapping product 2-hydroxyl terephthalic acid. And calculating the concentration of the hydroxyl radicals in the system to be detected according to the molar ratio of the 2-hydroxy terephthalic acid to the hydroxyl radicals of 1: 1. The method has the advantages of high sensitivity, few interference factors, strong specificity, accuracy, reliability, rapidness and online detection of the concentration of the hydroxyl radical.
Description
Technical Field
The invention relates to a method for detecting the concentration of hydroxyl radicals, in particular to a method for quantitatively detecting the hydroxyl radicals by using a laser flash photolysis technology.
Background
The hydroxyl radical (. OH) is next to fluorine (E)02.87V), and the oxidation-reduction potential of the oxidant reaches 2.80V, and the oxidant can initiate and induce a free radical chain reaction, directly react with various pollutants in water or atmosphere through electron transfer, electrophilic addition, dehydrogenation reaction and the like without selectivity, and finally degrade the pollutants into carbon dioxide, water and other harmless mineral salts. OH radicals have a short lifetime but are very reactive, whichThe reaction speed is very fast, the oxidation efficiency is high, and no secondary pollution is caused. Has been widely used in air pollution control and advanced treatment of wastewater in recent years.
Many research reports about quantitative detection methods of OH are reported at home and abroad, wherein the main methods comprise: (1) spin trapping-electron spin resonance spectroscopy (ESR) method; (2) chemical capture-High Performance Liquid Chromatography (HPLC) method; (3) oxidation reaction capture-spectrophotometry; (4) chemical trapping-fluorescence emission method, and the like. However, studies have shown that the spin trapping-ESR method can detect OH in real time, but generally the trapped product is unstable, has a short lifetime (only a few minutes to a few tens of minutes), is easy to quench, and has poor trapping agent specificity, ESR signal is unstable in decay with time, noise interference is severe, and sensitivity is low. Although the chemical capture-HPLC method has the characteristics of high pressure, high speed, high efficiency and high sensitivity, the HPLC method is complex and time-consuming to operate, a plurality of branch products exist in the reaction process, the measurement is interfered, and the existence of the stationary phase can cause various reactions of free radicals to quench the free radicals. The oxidation reaction capture-spectrophotometry and chemical capture-fluorescence method have the advantages of low instrument price, rapid analysis and simple operation, but the detection sensitivity is lower, the detection limit is higher, the specificity is not strong, and the interference factors are more. Therefore, there is still a need for improvement and improvement in the above-mentioned methods for accurate quantitative determination of OH due to the influence of the measurement system and the measurement conditions.
For nearly half a century, the Laser Flash Photolysis (LFP) technique has become one of the powerful tools for qualitatively or quantitatively studying transient intermediates (such as free radicals, ions, excited states, etc.) generated in photophysical or photochemical processes, and the LFP technique usually uses a strong pulse Laser light source to excite a sample to generate a photo-excited transient intermediate, and when the intermediate reaches a certain concentration, a characteristic transient absorption spectrum or emission spectrum is generated. The LFP technology is particularly suitable for researching low-concentration short-life transient intermediates, has extremely high sensitivity, and is widely applied to many scientific fields. Although studies of free radicals have been conducted for decades by the LFP technique, quantitative determination of OH by the LFP technique has not been reported.
Disclosure of Invention
The invention provides a method for quantitatively detecting OH by using a laser flash photolysis technology, aiming at the problems of low sensitivity, multiple interference factors, low specificity and the like in the conventional OH quantitative detection method. The method not only can quantitatively detect the concentration of OH, but also can investigate the transient emission lifetime and decay rate constant of a captured product.
The technical scheme of the invention is as follows:
a method for quantitatively detecting hydroxyl free radicals by utilizing a laser flash photolysis technology,
the trapping agent is terephthalic acid (PTA), and the molecular structural formula of the trapping agent is as follows:
after the capture agent captures OH (the capture agent and the OH react in a molar ratio of 1: 1), the only product 2-hydroxy terephthalic acid (2-HBDC) is generated, and the reaction formula is as follows:
from the above reaction, it can be seen that the hydrogen atom at the ortho position in the trapping agent PTA is replaced by. OH, and the concentration of the trapping product 2-HBDC is the same as that of. OH, namely:
C·OH＝C2-HBDC
the method comprises the following steps:
step 1: preparing 2-HBDC standard solutions with different concentrations, and measuring the characteristic transient emission spectrum of the 2-HBDC standard solutions with different concentrations by using a laser flash photolysis spectrometer, wherein the abscissa of the characteristic transient emission spectrum is wavelength, and the ordinate is transient emission intensity;
step 2: obtaining the transient emission intensity at the maximum emission wavelength according to the characteristic transient emission spectrum under each concentration obtained in the step 1, and drawing a standard curve of the corresponding relation between the concentration and the emission intensity of the 2-HBDC standard solution;
and step 3: during actual measurement, adding the PTA as a trapping agent in an excessive amount into a system to be measured for generating OH, generating OH in the system to be measured under the excitation of specific laser wavelength, reacting the PTA with the generated OH to generate 2-HBDC, and detecting the system to be measured by using a laser flash photolysis spectrometer to obtain a characteristic transient emission spectrum of the 2-HBDC; the specific laser wavelength is 266nm or 355nm, and the laser energy is 10-30 mJ;
and 4, step 4: and (3) obtaining the emission intensity at the maximum emission wavelength determined in the step (2) according to the characteristic transient emission spectrum of the system to be detected obtained in the step (3), further obtaining the concentration of the 2-HBDC in the system to be detected according to the standard curve obtained in the step (2), and obtaining the OH concentration according to the 1:1 molar ratio of the 2-HBDC to OH.
The concentration of the trapping agent PTA added into the system to be tested is 1-5 times of the generation concentration of OH.
The pH value range of the system to be detected is 7-14.
The pH value of the system to be detected is adjusted by NaOH or KOH.
The temperature range of the system to be measured is 20-70 ℃.
In the system to be detected, the range of the quantitatively detected OH concentration is 0.10-7.00 mu mol/L, when the OH concentration is more than 7.00 mu mol/L, the OH concentration is enabled to be in the range of 0.10-7.00 mu mol/L by diluting the system to be detected, and then the OH concentration of the diluted system to be detected is multiplied by the dilution times to obtain the OH concentration of the original system to be detected.
When the OH concentration (i.e., the concentration of the capture product 2-HBDC) is in the range of 0.10 to 7.00. mu. mol/L, the linear relationship between the OH concentration (i.e., the concentration of the capture product 2-HBDC) and the emission intensity is: y is 0.611X-0.035, linear correlation coefficient R2＝0.999；
Wherein Y is the emission intensity; the emission intensity is a quantum count value, without unit. X is the concentration of the capture product 2-HBDC, i.e., OH concentration, in. mu. mol/L. R2Is a linear correlation coefficient, R is an index for measuring the linear correlation degree between variables2Closer to 1, the better the linear correlation between the two variables.
In the system to be measured, the substance generating OH is hydrogen peroxide (H)2O2) Potassium persulfate (K)2S2O8) Sodium persulfate (Na)2S2O8) Potassium monopersulfate (2 KHSO)5·KHSO4·K2SO4) One or more than two of the above-mentioned materials are mixed, under the alkaline condition the sulfate radical can be reacted with hydroxide radical negative ion to produce OH.
The characteristic transient emission spectrum of the capture product 2-HBDC has the maximum emission wavelength of 431 nm.
The laser used by the laser flash photolysis spectrometer is a Quantel Nd YAG laser. The sensitivity of the instrument is high, and the detection limit Δ OD (RMS noise) of single sampling is 0.002 (fast detection mode) and 0.0005 (slow detection mode) respectively. The detector is an image enhancement type CCD, and the spectral response range is 200-850 nm.
The invention has the beneficial effects that: provides a novel method for quantitatively detecting OH by utilizing a laser flash photolysis technology. The method has the advantages of high sensitivity, few interference factors, strong specificity, accuracy, reliability, rapidness and capability of detecting the concentration of OH on line.
Drawings
FIG. 1 is a linear plot of hydroxyl radical concentration (0.10-7.00. mu. mol/L) versus transient emission intensity.
FIG. 2 is a characteristic transient emission spectrum of 2-hydroxyterephthalic acid.
FIG. 3 is a graph of the characteristic transient emission spectra of terephthalic acid before and after trapping of hydroxyl radicals.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Drawing of standard curve
Preparing a 2-HBDC standard solution, and selecting 6 different concentrations which are respectively as follows: 0.10. mu. mol/L, 0.40. mu. mol/L, 0.70. mu. mol/L, 1.00. mu. mol/L, 4.00. mu. mol/L, 7.00. mu. mol/L, and pH was adjusted to 9.1 with NaOH.
And (3) the standard solution is contained in a 1cm quartz cuvette, and the characteristic transient emission spectra of the 6 2-HBDC standard solutions with different concentrations are obtained by measuring with a laser flash photolysis spectrometer. The abscissa of the characteristic transient emission spectrum is wavelength, the ordinate is transient emission intensity, and the maximum emission wavelength is 431 nm.
And drawing a standard curve by taking the transient emission intensity as an ordinate and the 2-HBDC concentration as an abscissa.
(2) Regression equation derivation
Obtaining a regression equation according to the standard curve in the step (1): y is 0.611X-0.035, linear correlation coefficient R20.999. Wherein Y is the emission intensity and X is the concentration of 2-HBDC in mu mol/L. R2Is a linear correlation coefficient.
(3) Determination of OH concentration
Adding excessive PTA as trapping agent into OH-generating system to be tested, wherein the content of PTA is 1.00 mu mol/L H2O24 μmol/LPTA, system pH 9.1. Excited at a laser wavelength of 266nm, H2O2Photolyzing to generate OH, reacting PTA with generated OH to generate 2-HBDC, and detecting by laser flash photolysis spectrometer to obtain
Characteristic transient emission spectrum of 2-HBDC.
From the characteristic transient emission spectrum, it was confirmed that the emission intensity value at the maximum emission wavelength of 431nm was 0.94, and the concentration of 2-HBDC was 1.60. mu. mol/L as calculated from the regression equation of step (2). According to the molar ratio relationship between 2-HBDC and OH1:1, the OH concentration is 1.60 mu mol/L. At the same time, H2O2The photolysis efficiency of (a) was 80%.
Example 2
(1) Drawing of standard curve
The same as in example 1.
(2) Regression equation derivation
The same as in example 1.
(3) Determination of OH concentration
Adding excess trapping agent PTAInto a system to be tested which generates OH, wherein the content of the OH is 2.00 mu mol/L H2O27 μmol/LPTA, system pH 9.1. Excited at a laser wavelength of 266nm, H2O2And H, photolyzing to generate OH, reacting PTA with the generated OH to generate 2-HBDC, and detecting by a laser flash photolysis spectrometer to obtain the characteristic transient emission spectrum of the 2-HBDC.
From the characteristic transient emission spectrum, it was confirmed that the value of the emission intensity at the maximum emission wavelength of 431nm was 1.92, and the concentration of 2-HBDC was 3.20. mu. mol/L as calculated from the regression equation of step (2). According to the molar ratio relationship between 2-HBDC and OH1:1, the OH concentration is 3.20 mu mol/L. At the same time, H2O2The photolysis efficiency of (a) was 80%.
Claims (7)
1. A method for quantitatively detecting hydroxyl free radicals by utilizing a laser flash photolysis technology is characterized in that after a trapping agent PTA captures OH, hydrogen atoms on ortho positions in PTA are replaced by OH to generate a unique product 2-hydroxyl terephthalic acid 2-HBDC, and the reaction formula is as follows:
from the above reaction, it is seen that the concentration of the capture product 2-HBDC is the same as the concentration of. OH, namely:
C·OH＝C2-HBDC
the method comprises the following steps:
step 1: preparing 2-HBDC standard solutions with different concentrations, and measuring the characteristic transient emission spectrum of the 2-HBDC standard solutions with different concentrations by using a laser flash photolysis spectrometer, wherein the abscissa of the characteristic transient emission spectrum is wavelength, and the ordinate is transient emission intensity;
step 2: obtaining the transient emission intensity at the maximum emission wavelength of 431nm according to the characteristic transient emission spectrum under each concentration obtained in the step 1, and drawing a standard curve of the corresponding relation between the concentration of the 2-HBDC standard solution and the emission intensity;
and step 3: during actual measurement, adding the trapping agent PTA in an excessive amount into a system to be measured for generating OH, wherein the concentration of the trapping agent PTA added into the system to be measured is 1-5 times of the generation concentration of OH, generating OH in the system to be measured under the excitation of specific laser wavelength, reacting the trapping agent PTA with the generated OH to generate 2-HBDC, and detecting the system to be measured by using a laser flash photolysis spectrometer to obtain a characteristic transient emission spectrum of the 2-HBDC; the specific laser wavelength is 266nm or 355nm, and the laser energy is 10-30 mJ;
and 4, step 4: and (3) obtaining the emission intensity at the maximum emission wavelength determined in the step (2) according to the characteristic transient emission spectrum of the system to be detected obtained in the step (3), further obtaining the concentration of the 2-HBDC in the system to be detected according to the standard curve obtained in the step (2), and obtaining the OH concentration according to the 1:1 molar ratio of the 2-HBDC to OH.
2. The method of claim 1, wherein the pH value of the system to be tested is 7-14, and is adjusted by NaOH or KOH; the temperature of the system to be measured is 20-70 ℃.
3. The method of claim 1, wherein in the system to be tested, the range of the quantitatively-detected-OH concentration is 0.10-7.00 μmol/L, when the-OH concentration is greater than 7.00 μmol/L, the-OH concentration is made to be in the range of 0.10-7.00 μmol/L by diluting the system to be tested, and then the-OH concentration of the diluted system to be tested is multiplied by the dilution multiple to obtain the-OH concentration of the original system to be tested;
when the OH concentration is in the range of 0.10 to 7.00. mu. mol/L, the linear relationship of OH concentration to emission intensity is: y is 0.611X-0.035, linear correlation coefficient R2＝0.999；
Wherein Y is emission intensity, and the emission intensity is a quantum count value without a unit; x is the concentration of the capture product 2-HBDC, namely. OH concentration, and the unit is mu mol/L; r2Is a linear correlation coefficient, R is an index for measuring the linear correlation degree between variables2Closer to 1, the better the linear correlation between the two variables.
4. The method according to claim 2, wherein the range of the-OH concentration of the quantitative determination in the system to be tested is 0.10-7.00. mu. mol/L, and when the-OH concentration is greater than 7.00. mu. mol/L, the-OH concentration is adjusted to be in the range of 0.10-7.00. mu. mol/L by diluting the system to be tested, and then the-OH concentration of the diluted system to be tested is multiplied by the dilution factor to obtain the-OH concentration of the original system to be tested.
5. The method according to claim 1 or 4, wherein the substance generating OH in the system under test is one or a mixture of two or more of hydrogen peroxide, potassium persulfate, sodium persulfate and potassium monopersulfate, and the sulfate radical reacts with hydroxide anion under alkaline conditions to generate OH.
6. The method according to claim 2, wherein the substance generating OH in the system under test is one or a mixture of two or more of hydrogen peroxide, potassium persulfate, sodium persulfate and potassium monopersulfate, and the sulfate radical reacts with hydroxide anion under alkaline conditions to generate OH.
7. The method according to claim 3, wherein the substance generating OH in the system under test is one or a mixture of two or more of hydrogen peroxide, potassium persulfate, sodium persulfate and potassium monopersulfate, and the sulfate radical reacts with hydroxide anion under alkaline conditions to generate OH.
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| CN109765219B (en) * | 2019-01-11 | 2021-04-27 | 四川大学 | Chemiluminescence probe for detecting hydroxyl free radicals in atmospheric particulates and sensing analysis method thereof |
| CN110361358B (en) * | 2019-07-10 | 2020-08-28 | 中山大学 | Method for quantitatively detecting chlorine free radical and determining secondary reaction rate constant thereof by laser flash photolysis |
| CN111081580A (en) * | 2019-08-23 | 2020-04-28 | 德淮半导体有限公司 | Method for detecting broken bond strength of wafer |
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