CN107607600B - Detection of catechol and NO2-sensor, method of construction and use thereof - Google Patents
Detection of catechol and NO2-sensor, method of construction and use thereof Download PDFInfo
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- CN107607600B CN107607600B CN201710712326.0A CN201710712326A CN107607600B CN 107607600 B CN107607600 B CN 107607600B CN 201710712326 A CN201710712326 A CN 201710712326A CN 107607600 B CN107607600 B CN 107607600B
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Abstract
The invention provides a method for detecting catechol and NO2The method of constructing an electrochemical sensor of (1), comprising the steps of: (1) placing the nitrogen-sulfur co-doped multiwalled carbon nanotube into a chitosan acetic acid solution, adding reflux treatment, cleaning and drying the obtained solid with water, and dispersing the solid in the water; (2) polishing the glassy carbon electrode by using alumina powder, activating in acid, dripping the substance obtained in the step (1), and drying; (3) immersing the electrode obtained in the step (2) in HAuCl4(KNO3) In the electrolyte, gold nano-particles are laminated on the surface of the electrode by a chronoamperometry, thus obtaining the electrode. The sensor has the advantages of large specific surface area, good conductivity and simple and convenient preparation method. Compared with the prior art, the method can obviously improve the detection electric signal, the analysis selectivity and the sensitivity, the catechol linear range is 1-5000 mu M, and NO is2The linear range is 1 to 7000. mu.M.
Description
Technical Field
The present invention belongs to catechol and NO2 -The field of detection, and relates to construction and application of a modified electrode in an electrochemical sensor.
Background
Catechol is widely used in textile, dye, plastic, petroleum refinery, cosmetics, antioxidant, pesticide and other fields. However, catechol leaks and is released into the environment during processing and application in these fields, has a strong irritating effect on the skin, eyes, etc., is harmful to aquatic organisms, may have a long-term adverse effect on the water environment, and may have a risk of irreversible consequences. NO2 -The food additive is widely applied to food technology and used as a food additive to prevent food from rotting so as to prolong the shelf life of the food. But NO2 -Can easily form methemoglobin with hemoglobin, and react with secondary amine to form mutagenic, teratogenic and carcinogenic substances, and cause gastric cancer and esophageal cancer. For catechol and NO2 -Although the existing analysis technology shows good selectivity and sensitivity, the detection method has the defects of expensive equipment, complex pretreatment and detection process and the like.
Therefore, it is urgently needed to establish a simple and rapid detection method.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide a method for detecting catechol and NO2 -The method for constructing an electrochemical sensor, comprising the steps of:
(1) placing the nitrogen-sulfur co-doped multiwalled carbon nanotube into a chitosan acetic acid solution, carrying out heating reflux treatment, cleaning and drying the obtained solid with water, and dispersing the solid in the water;
(2) performing sub-polishing treatment on the glassy carbon electrode by using alumina powder, activating in acid, dropwise adding the product obtained in the step (1), and then performing drying treatment;
(3) immersing the electrode obtained in the step (2) in a solution containing HAuCl4And KNO3In the electrolyte, gold nano-particles are laminated on the surface of the electrode by a chronoamperometry, thus obtaining the electrode.
The invention improves the p-catechol and NO through preparing the excellent nano material modified electrode2 -Sensitivity and selectivity of detection.
In the invention, the gold nanoparticles (AuNPs) have good mechanical property and conductivity and larger active surface area so as to improve biological components attached to the sensing surface. The multi-walled carbon nanotube (MWCNT) has unique physicochemical properties such as high specific surface area, chemical stability and the like, and is an excellent electrode material.
"1 mM HAuCl" according to the present invention4(0.1M KNO3) The preparation method of the electrolyte comprises the following steps: potassium nitrate was added to the aqueous chloroauric acid solution so that the concentration of chloroauric acid was 1mM HAuCl4The concentration of potassium nitrate was 0.1M.
The invention dopes N, S and other elements into MWCNT to improve conductivity and hydrophilicity. In the invention, due to the characteristics of hydrophilicity and high porosity of Chitosan (CS), the steric hindrance and mass transfer resistance of the nano material can be reduced.
In the electrochemical oxidation process, catechol and NO2 -Oxidation easily occurs, electrons are lost, and an electrochemical signal is generated.
The invention constructs catechol and NO with high sensitivity and selectivity2 -The sensor is prepared on the basis of a composite material (AuNPs/CS @ N, S-MWCNTS) consisting of nitrogen and sulfur co-doped carbon nano tube loaded chitosan and gold nano particles. According to experimental verification, the method can be applied to analysis of catechol in water and NO in food2 -The analysis of (2) and the effect is remarkable.
In the prior art prior to the present invention, many techniques were only well able to detect an objectThe method not only has excellent detection capability on catechol, but also can well detect NO2 -。
It is worth noting that the present invention has an excellent linear range for catechol detection, and when the catechol reaches 5000. mu.M, the accuracy of the detection is not affected.
In addition, the chitosan and HAuCl4 used in the invention are easily available raw materials, and the raw materials are low in cost.
In the step (1), the preparation method of the nitrogen and sulfur co-doped multi-walled carbon nanotube comprises the following steps: placing multi-walled carbon nanotubes in HNO3And H2SO4Heating and refluxing the mixed acid, grinding the mixed acid and thiourea together, putting the mixture into a tube furnace, and introducing N2Calcining under the condition of (1) to obtain the catalyst.
Preferably, in the step (1), the temperature of the reflux treatment is 90 ℃, and the reflux time is 8 h.
In the step (1), the water is deionized water; andor, the volume fraction of the acetic acid solution is 2%.
Preferably, the concentration of the product obtained in the step (1) is 1 mg/mL.
Preferably, in the step (2), the dropwise adding amount of the product obtained in the step (1) is 10 μ L; and or, the drying method is natural drying at normal temperature.
Preferably, in the step (3), the electrolyte is 1mM HAuCl4(0.1M KNO3)。
Preferably, in the step (3), the gold nano-particles are laminated on the surface of the electrode by a chronoamperometry method for 200 seconds from-0.2V to 0V.
It is another object of the present invention to provide an electrochemical sensor prepared by the above method.
It is still another object of the present invention to provide the above electrochemical sensor for detecting catechol and NO2 -Application of the aspect. In particular, the application is catechol in water and NO in food2 -The detection conditions are as follows: measurement Medium: phosphate buffer at pH 7.4; and (3) detecting the potential: +0.3V, + 0.9V; electrochemical detection method: amperometric response method.
Preferably, when the nitrogen-sulfur co-doped multi-walled carbon nanotube is prepared, the reflux temperature is 75 ℃, and the treatment time is 3 hours; the calcining temperature is 350 ℃, and the treatment time is 1 h.
The invention has the beneficial effects that:
the sensor obtained by the invention has the advantages of large specific surface area, good conductivity and simple and convenient preparation method. Compared with the prior art, the method can obviously improve the selectivity and the sensitivity of the detected electric signals and analysis, the linear range of catechol is 1 to 5000 MuM, and NO is2 -The linear range is 1 to 7000. mu.M.
Drawings
FIG. 1: the preparation flow chart of AuNPs/CS @ N, S co-doped MWCNTS composite material.
FIG. 2: transmission electron microscope and scanning electron microscope images of the nano-material: (A) AuNPs, (B) AuNPs/N, Sco-coped MWCNTS and (C) AuNPs/CS @ N, Sco-coped MWCNTS scanning electron micrographs; transmission Electron microscopy of (D, E) N, S co-sequenced MWCNTs and (F, G) CS @ N, S co-sequenced MWCNTs.
FIG. 3: (a) the sensor of the invention continuously adds the ampere response graphs (voltage: +0.2V) of pyrocatechol with different concentrations; (b) the current response is plotted as a linear result of catechol concentration.
FIG. 4: (a) the sensor of the invention continuously adds NO with different concentrations2 -Ampere response diagram (voltage: + 0.9V); (b) is current response and NO2 -Linear results plot of concentration.
FIG. 5: when the sensor detects catechol: (a) response time, (b) amperometric detection results for different interferents.
FIG. 6: detection of NO by the sensor of the present invention2 -The method comprises the following steps: (a) amperometric detection results for different interferents, (b) reproducibility.
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
1) Synthesizing N, S-MWCNTS nano material: MWCNTS in HNO3And H2SO4Heating and refluxing the mixed acid to carboxylate the mixed acid; then grinding the mixture together with thiourea, placing the mixture into a tube furnace, and calcining the mixture for a certain time under the condition of introducing N2 to obtain the N, S-MWCNTS nano material.
2) CS @ N, S-MWCNTS nano material synthesis: dissolving a certain amount of chitosan in 2% acetic acid, adding the N, S-MWCNTS obtained in the step 1), uniformly stirring, heating and refluxing for 8 hours, cleaning the obtained solid with deionized water, drying, and dispersing in the deionized water to form 1mg/mL black dispersion for later use.
3) Preparing an AuNPs/CS @ N, S-MWCNTS modified electrode: polishing a glassy carbon electrode by using alumina powder, activating in acid, then dropwise adding 10 mu L of the dispersion liquid obtained in the step 2) on the surface of the glassy carbon electrode, and naturally drying at room temperature. The resulting electrode was immersed in 1mM HAUCL4In an electrolyte solution of (0.1M KNO3), gold nanoparticles were deposited on the electrode surface by a chronoamperometry method for 200 seconds from-0.2V to 0V. And finally, obtaining the glassy carbon electrode modified by AuNPs/CS @ N, S-MWCNTS.
Example 2
1) Synthesizing N, S-MWCNTS nano material: MWCNTS in HNO3And H2SO4Heating and refluxing the mixed acid to carboxylate the mixed acid; then grinding the mixture together with thiourea, placing the mixture into a tube furnace, and introducing N2Calcining for a certain time under the condition of (1) to obtain the N, S-MWCNTS nano material.
2) CS @ N, S-MWCNTS nano material synthesis: dissolving a certain amount of chitosan in 2% acetic acid, adding the N, S-MWCNTS obtained in the step 1), uniformly stirring, heating and refluxing for 8 hours, cleaning the obtained solid with deionized water, drying, and dispersing in the deionized water to form 1mg/mL black dispersion for later use.
3) Preparing an AuNPs/CS @ N, S-MWCNTS modified electrode: polishing glassy carbon electrode with alumina powder, activating in acid, and dripping the components obtained in step 2) on the surfaceThe dispersion was 10. mu.L, and was naturally dried at room temperature. The resulting electrode was immersed in 1mM HAUCL4(0.1M KNO3) In the electrolyte, gold nanoparticles were deposited on the electrode surface by a chronoamperometry method for 200 seconds from-0.2V to 0V. And finally, obtaining the glassy carbon electrode modified by AuNPs/CS @ N, S-MWCNTS.
Example 3
1) Synthesizing N, S-MWCNTS nano material: MWCNTS in HNO3And H2SO4Heating and refluxing the mixed acid to carboxylate the mixed acid; then grinding the mixture together with thiourea, placing the mixture into a tube furnace, and introducing N2Calcining for a certain time under the condition of (1) to obtain the N, S-MWCNTS nano material.
2) CS @ N, S-MWCNTS nano material synthesis: dissolving a certain amount of chitosan in 2% acetic acid, adding the N, S-MWCNTS obtained in the step 1), uniformly stirring, heating and refluxing for 8 hours, cleaning the obtained solid with deionized water, drying, and dispersing in the deionized water to form 1mg/mL black dispersion for later use.
3) Preparing an AuNPs/CS @ N, S-MWCNTS modified electrode: polishing a glassy carbon electrode by using alumina powder, activating in acid, then dropwise adding 10 mu L of the dispersion liquid obtained in the step 2) on the surface of the glassy carbon electrode, and naturally drying at room temperature. The resulting electrode was immersed in 1mM HAUCL4(0.1M KNO3) In the electrolyte, gold nanoparticles were deposited on the electrode surface by a chronoamperometry method for 200 seconds from-0.2V to 0V. And finally, obtaining the glassy carbon electrode modified by AuNPs/CS @ N, S-MWCNTS.
The practical application is as follows: the electrochemical sensor of the invention is used for detecting the actual sample containing catechol or NO2 -Calculated by an amperometric response method and combined with a standard recovery method, and the results are shown in tables 1 and 2. Each sample is measured in parallel for 3 times, and the RSD value is lower than 3 percent, which shows that the reproducibility of the sensor is good. The recovery rate of the added standard is 89.60% -106.10%, which shows that the sensor can be used for detecting actual samples, and the invention can be used for detecting catechol and NO2 -The method of (3) is reliable.
Table 1 shows the results of measuring catechol in water sample by using the sensor of the present invention
TABLE 2 measurement of NO in food by the sensor of the present invention2 -Measurement result of (2)
Claims (10)
1. Detection of catechol and NO- 2The method for constructing an electrochemical sensor, comprising the steps of:
(1) placing the nitrogen-sulfur co-doped multiwalled carbon nanotube into a chitosan acetic acid solution, carrying out heating reflux treatment, cleaning and drying the obtained solid with water, and dispersing the solid in the water;
(2) polishing a glassy carbon electrode by using alumina powder, activating in acid, dripping the substance obtained in the step (1), and drying;
(3) immersing the electrode obtained in the step (2) in a solution containing HAuC14And KNO3In the electrolyte, gold nano is deposited on the surface of the electrode by a timing current method, and the electrode is obtained;
in the step (1), the preparation method of the nitrogen and sulfur co-doped multi-walled carbon nanotube comprises the following steps: placing multi-walled carbon nanotubes in HNO3And H2SO4Heating and refluxing the mixed acid, grinding the mixed acid and thiourea together, putting the mixture into a tube furnace, and introducing N2Calcining under the condition of (1) to obtain the catalyst.
2. The method according to claim 1, wherein in the step (1), the temperature of the reflux treatment is 90 ℃ and the reflux time is 8 h.
3. The method according to claim 1, wherein in step (1), the water is deionized water; the volume fraction of the acetic acid solution is 2%.
4. The method according to claim 1, wherein the concentration of the product obtained in step (1) is 1 mg/mL.
5. The method according to claim 1, wherein in the step (2), the dropwise addition amount of the product obtained in the step (1) is 10 μ L; the drying method is natural drying at normal temperature.
6. The method of claim 1, wherein step (3) comprises 1mM HAuCl per liter of electrolyte4And 0.1M KNO3。
7. The method of claim 1, wherein the gold nanoparticles are deposited on the surface of the electrode by a chronoamperometry method for 200 seconds from-0.2V to 0V.
8. The method according to claim 2, wherein the reflux temperature is 75 ℃ and the treatment time is 3h when preparing the nitrogen-sulfur co-doped multi-walled carbon nanotubes; the calcining temperature is 350 ℃, and the treatment time is 1 h.
9. An electrochemical sensor prepared according to any one of claims 1 to 8.
10. The electrochemical sensor of claim 9 for detecting catechol and NO- 2The application of the aspect is that the application is catechol in water and NO in food- 2The detection conditions are as follows: measurement Medium: phosphate buffer at pH 7.4; and (3) detecting the potential: +0.3V, + 0.9V; the detection electrochemical method comprises the following steps: amperometric response method.
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| CN103592337A (en) * | 2013-11-19 | 2014-02-19 | 山东理工大学 | Pesticide multiresidue detection method based on array type sensor |
| CN103592437A (en) * | 2013-11-11 | 2014-02-19 | 山东理工大学 | Immunosensor based on modification of graphene-multiwalled carbon-nanogold size-chitosan |
| CN105006375A (en) * | 2015-06-04 | 2015-10-28 | 郑州大学 | Nitrogen and phosphor co-doped porous carbon nanotube, and preparation method and application thereof |
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| CN103592437A (en) * | 2013-11-11 | 2014-02-19 | 山东理工大学 | Immunosensor based on modification of graphene-multiwalled carbon-nanogold size-chitosan |
| CN103592337A (en) * | 2013-11-19 | 2014-02-19 | 山东理工大学 | Pesticide multiresidue detection method based on array type sensor |
| CN105006375A (en) * | 2015-06-04 | 2015-10-28 | 郑州大学 | Nitrogen and phosphor co-doped porous carbon nanotube, and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
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| Enhancement of nitrogen and sulfur co-doping on the electrocatalytic properties of carbon nanotubes for VO2+/VO2;Chuanchang Li等;《The Royal Society of Chemistry 2017》;20170224;第7卷;第3591-3601页 * |
| Simultaneous voltammetric determination of hydroquinone and catechol by using a glassy carbon electrode modified with carboxy-functionalized carbon nanotubes in a chitosan matrix and decorated with gold nanoparticles;Yu Shen等;《Microchim Acta》;20170629;第184卷;第13184-13190页 * |
| 一步法电沉积制备纳米金／碳纳米管修饰电极及对邻苯二酚电催化性能研究;冯莉 等;《江西化工》;20120330(第1期);第97-101页 * |
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