CN101949880B - Functionalized mesoporous material modified electrode and method for measuring benzenediol isomerides - Google Patents
Functionalized mesoporous material modified electrode and method for measuring benzenediol isomerides Download PDFInfo
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Abstract
The invention relates to the technical field of chemical isomeride analysis and measurement, in particular to a functionalized mesoporous material modified electrode and a method for simultaneously measuring three isomerides of benzenediol by using the same. The invention comprises the preparation of the functionalized mesoporous material modified electrode, and an operation method for simultaneously measuring three isomerides of the benzenediol by using the electrode. By adopting a functionalized mesoporous material to prepare the modified electrode, the invention has the advantages of simple and convenient material synthesis, simple and convenient electrode preparation, low material price, easy electrode update, good repeatability, no toxicity and no pollution to the environment, and the measurement method has good selectivity and high sensitivity.
Description
Technical Field
The invention relates to the technical field of chemical isomer analysis and determination, in particular to a functionalized modified electrode utilizing a mesoporous material and a method for simultaneously determining three isomers of benzenediol by utilizing the functionalized modified electrode.
Background
The benzenediol is an important chemical raw material and is widely applied to the industries of photographic developers, synthetic dyes, cosmetics, plastics, leather making, chemistry, pharmacy and the like in daily production and life. Meanwhile, it is an organic pollutant with high toxicity and has great harm to human body and environment. The diphenol isomer is a common coexisting isomer, the chemical and physical properties of the diphenol isomer and the isomer are similar, the three are difficult to distinguish by a common determination method, and the diphenol isomer, the isomer and the isomer are mostly prepared by a high performance liquid chromatography, a pH flow injection analysis method, a fluorescence quenching method, a biosensor and the like at present. However, these methods generally require pretreatment of the sample, are complicated and time-consuming to operate, require a large number of supporting devices, and are difficult to implement on-site emergency monitoring and on-line analysis. In recent years, more and more analysts have utilized chemically modified electrodes to achieve simultaneous determination of hydroquinone isomers, such as: single-walled carbon nanotubes, mesoporous platinum, carbon nanotube bromophenol blue polymeric membranes, mesoporous carbon, and the like. At present, electrochemical detection of hydroquinone isomer mainly focuses on electrocatalytic oxidation on polypyrrole films and polyaniline film electrodes and catalytic oxidation on carbon nanotube electrodes. In these methods, the electrode materials used are complex to synthesize and expensive; the technical requirements for electrode surface modification are strict, the preparation is difficult, the electrode is not easy to update, and the reproducibility is poor; and the peak potentials of the o-dihydroxybenzene and the p-dihydroxybenzene are very close to each other, so that the o-dihydroxybenzene and the p-dihydroxybenzene cannot be effectively separated, the linear range is narrow, and the detection selectivity and the sensitivity are not high. Therefore, it is highly desirable to establish a fast, convenient, highly selective and highly sensitive electrochemical assay for simultaneously determining three isomers of benzenediol. The method has important significance in the fields of environmental monitoring, chemical industrial production, online quality monitoring and the like.
The mesoporous silicon oxide material has the characteristics of long-range ordered pore channels, high porosity, large specific surface, narrow distribution, continuously adjustable pore diameter in a certain range and the like. The silicon-based mesoporous material skeleton is mainly made of amorphous SiO2Therefore, the surface chemistry of the mesoporous material is relatively close to that of amorphous silica gel, and a considerable number of silanol bonds (Si-OH) exist on the surface. A large amount of silicon hydroxyl on the surface of the mesoporous material is easy to carry out surface functionalization. After organic groups are introduced into the nanometer pore canal of the pure silicon mesoporous material, the original texture performance of the pure silicon mesoporous material is kept, meanwhile, the interface hydrophobicity of the mesoporous pore canal is improved, and the hydrothermal stability of the mesoporous material is favorably improved. The organic group modification on the surface of the material can enable the surface of the mesoporous silicon to have specific functional groups, thereby endowing the mesoporous silicon with special properties and expanding the application range of the mesoporous material in the aspects of immobilized homogeneous catalysts, adsorption separation, molecular recognition, chemical sensing and the like. The chemically modified electrode is formed by performing molecular design on the surface of the electrode, and fixing molecules, ions and polymers with excellent chemical properties on the surface of the electrode, so that the electrode has certain specific chemical and electrochemical properties. The chemically modified electrode is applied to analysis, has wide prospect, and can play an increasingly larger role in the determination of inorganic matters, organic matters and biological samples. The mesoporous material chemically modified electrode has the advantages of ordered mesoporous materialThe large specific surface area and the orderly arranged pore diameters can promote the rapid migration of electroactive substances and the transfer of electrons in the pore channels, and can carry out selective catalysis.
Disclosure of Invention
The invention aims to provide a functional modified electrode by utilizing mesoporous materials and a method for simultaneously determining three isomers of benzenediol by utilizing the functional modified electrode, aiming at the defects in the determination, the functional preparation of the modified electrode by utilizing the mesoporous materials has the advantages of simple and convenient material synthesis, simpler and more convenient electrode preparation, low material price, easy electrode updating, good reproducibility, no toxicity, no environmental pollution, high sensitivity and good selectivity.
The technical scheme of the invention is as follows: a mesoporous material modified electrode is prepared from mesoporous material NH2SBA15 and graphite powder were used to prepare electrodes and to determine three isomers of benzenediol simultaneously.
The mesoporous material modified electrode comprises the specific manufacturing steps of weighing graphite powder and a mesoporous material NH according to the mass ratio of 5:12Adding SBA15 into agate mortar, shaking while dripping liquid paraffin to form a tough smaller sheet, placing into a glass tube, compacting, winding a black adhesive tape on a copper wire to be taken as a lead, leading out, polishing the other end on smooth and clean weighing paper, and washing with secondary redistilled water to obtain the amino-functionalized SBA-15 mesoporous material modified electrode (NH)2SBA15/CPE), when the surface needs to be renewed, extruding the carbon paste for 2-3 mm, polishing the carbon paste on weighing paper, and cleaning.
The electrode (NH) is modified by the functional mesoporous material2SBA15/CPE) to determine the three isomers of benzenediol,
precisely transferring certain amounts of o-dihydroxybenzene (CC), m-dihydroxybenzene (RC) and p-dihydroxybenzene (HQ) solution into an electrolytic cell containing 10mL of phosphate buffer solution (pH6.0) by using a micropipetteWith the electrode NH2SBA15/CPE as working electrode, Ag/AgCl electrode as reference electrode, and platinum electrode as counter electrode; the experiment is carried out on a CHI842B electrochemical comprehensive tester, and the attached computer software is used for collecting and processing experimental data; differential pulse scanning is carried out within the potential range of-0.4-0.8V, and a stable differential pulse voltammogram is recorded;
② the concentrations of o-dihydroxybenzene, m-dihydroxybenzene and p-dihydroxybenzene are respectively fixed at 2X 10-6Changing one of the concentrations by mol/L, and increasing the oxidation peak current along with the increase of the concentration to obtain a linear relation curve of the o-benzenediol, the m-benzenediol and the p-benzenediol; simultaneously, according to the determination principle of the relevant sensitivity, the detection limits of the three are determined;
the best conditions for measuring the isomers of the benzenediol are as follows: KH is selected as supporting electrolyte2PO4-Na2HPO4Solution (PBS) buffer, pH6.0 optimal. The concentration of three isomers measured by a differential pulse method and a differential pulse method is in a good linear relation with peak current in a certain range;
the linear range of p-dihydroxybenzene was 1.0X 10-6～1.6×10-4mol/L, linear equation of Ip=-16.9321-0.1224×106c, c is concentration in mol/L, peak current IpThe unit is mA, the linear correlation coefficient r = -0.9992, and the detection limit is 2.0 multiplied by 10-7mol/L；
The linear range of o-dihydroxybenzene was 2.0X 10-6～1.0×10-4mol/L, linear equation of Ip=-2.0763-0.0064×106c, c is concentration in mol/L, peak current IpThe unit is mA, the linear correlation coefficient r = -0.9998, and the detection limit is 2.0 multiplied by 10-7 mol/L；
The linear range of m-dihydroxybenzene is 5.0X 10-6～1.4×10-4mol/L, linear equation of Ip=-24.6716-0.0333×106c, c is concentration in mol/L, peak current IpThe unit is mA, and the linear correlation coefficient r = -0.9995, detection limit of 5.0X 10-7mol/L；
Combining the linear equation to determine the benzenediol isomer mixture solution sample with unknown concentration and calculate the concentration of each isomer; placing the three-component mixed solution of the ortho-dihydroxybenzene, the meta-dihydroxybenzene and the para-dihydroxybenzene with unknown concentration into an electrolytic cell, and placing the electrode NH2SBA15/CPE as working electrode, Ag/AgCl electrode as reference electrode, and platinum electrode as counter electrode; the experiment is carried out on a CHI842B electrochemical comprehensive tester, and the attached computer software is used for collecting and processing experimental data; differential pulse scanning is carried out in the potential range of-0.4-0.8V, and I of different isomers is respectively measured at different peak potentialsPA value; measuring the measured IPAnd substituting the values into the linear equation to calculate the respective concentrations of the o-nitrophenol, the m-nitrophenol and the p-nitrophenol.
The invention has the beneficial effects that: the electrode material is functionally modified by the mesoporous material, and has the advantages of simple and convenient synthesis, simple and convenient electrode manufacture, low material price, easy electrode updating, good reproducibility, no toxicity and no environmental pollution; and the determination method has high sensitivity and good selectivity. The difference between the oxidation peak potentials of the p-benzenediol and the o-benzenediol is 120 mV, and the difference between the oxidation peak potentials of the o-benzenediol and the m-benzenediol is 350 mV, so that three isomers of the benzenediol can be obviously distinguished.
Description of the drawings:
FIG. 1 is a differential pulse voltammogram of a benzenediol isomer at different electrodes;
FIG. 2 is a graph showing the differential pulse voltammograms of ortho-diphenol (CC) at different concentrations;
FIG. 3 is a graph showing the differential pulse voltammograms of m-dihydroxybenzene (RC) at different concentrations;
FIG. 4 shows the differential pulse voltammogram of p-dihydroxybenzene (HQ) at different concentrations.
Wherein,1-o-benzenediol (CC), 2-m-benzenediol (RC), 3-p-benzenediol (HQ) 4-pure Carbon Paste Electrode (CPE), 5-SBA15 modified electrode (SBA 15/CPE), 6-electrode of the invention (NH)2-SBA15/CPE）
The specific implementation mode is as follows:
for better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto.
Example 1
1. Mesoporous material NH2Synthesis of SBA15
Synthesis of SBA-15
References to the synthetic procedure of SBA-15 report: SBA15 was synthesized as P123(Aldrich, EO)20PO70EO20Ma =5800) is a structure directing agent. 3.286 g P123 is taken to be dissolved in 30 g of deionized water, 98 g of 2 mol/L HCl solution is added, the solution is stirred at 40 ℃ until the solution is transparent, 6.944 g of TEOS is dropwise added, the solution is stirred and crystallized at 40 ℃ for 24 hours, and then the solution is transferred to an aging bottle to be kept stand and aged at 80 ℃ for 48 hours. And (4) carrying out suction filtration, washing the product to be neutral by secondary redistilled water and ethanol in sequence, and transferring the product to a vacuum box for drying. And (3) heating the dried product to 550 ℃ at the speed of 1 ℃/min in a box-type high-temperature resistance furnace, and calcining for 6 h to obtain the SBA-15 product for later use. The molar ratio of the raw materials used in the experiment is about n (TEOS): n (P123): n (HCl): n (H)2O) = 1:0.017:5.8:181。
② surface amination modification of mesoporous material SBA15
The synthesis of the aminated SBA-15 comprises the following steps: adding 1.0 g of SBA-15 into a three-necked bottle, adding 30 mL of anhydrous toluene, stirring uniformly at room temperature, and then2.5 mL of APTES was slowly added dropwise, stirring was continued for 1 h, the temperature was raised to 70 ℃ and reflux was carried out for 18 h. After reaction, obtaining a product by suction filtration, washing the product with toluene and isopropanol for three times respectively, and drying the product in vacuum at 150 ℃ for 10 hours to obtain NH2-SBA15。
2．NH2Preparation of-SBA 15/CPE modified electrode
Functionalized mesoporous material modified electrode (NH)2-SBA15/CPE), production steps: weighing 1.0 g of graphite powder and 0.2 g of functional mesoporous material NH2SBA15 is put into an agate mortar, liquid paraffin is dripped while shaking up to form a tough smaller sheet-shaped object, then the small sheet-shaped object is put into a glass tube with the diameter of about 5mm, the glass tube is pressed by a thin glass rod, a black adhesive tape is wound on a copper wire to be taken as a lead to be led out, the other end of the glass tube is polished on smooth and clean weighing paper, and the amino functional SBA-15 mesoporous material modified electrode (NH) required by the experiment is prepared by washing with secondary water2SBA 15/CPE). And when the surface needs to be renewed, extruding the carbon paste for 2-3 mm, polishing the carbon paste on weighing paper, and cleaning.
3. Determination of three isomers of benzenediol:
accurately transferring a certain amount of o-dihydroxybenzene, m-dihydroxybenzene and p-dihydroxybenzene solution into an electrolytic cell containing 10mL of phosphate buffer solution (pH6.0) by using a micropipette, wherein the electrode in claim 1 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, and a platinum electrode is used as a counter electrode; the experiment is carried out on a CHI842B electrochemical comprehensive tester, and the attached computer software is used for collecting and processing experimental data; differential pulse scanning is carried out within the potential range of-0.4-0.8V, and a stable differential pulse voltammogram is recorded;
② the concentrations of o-dihydroxybenzene, m-dihydroxybenzene and p-dihydroxybenzene are respectively fixed at 2X 10-6Changing one of the concentrations by mol/L, and increasing the oxidation peak current along with the increase of the concentration to obtain a linear relation curve of ortho-hydroquinone, meta-hydroquinone and hydroquinone; simultaneously, according to the determination principle of the relevant sensitivity, the detection limits of the three are determined;
determination of benzeneThe best conditions for the diphenol isomers are: KH is selected as supporting electrolyte2PO4-Na2HPO4Solution (PBS) buffer, pH6.0 optimal. The concentration of three isomers measured by a differential pulse method and a differential pulse method is in a good linear relation with peak current in a certain range;
the linear range of p-dihydroxybenzene was 1.0X 10-6～1.6×10-4mol/L, linear equation of Ip=-16.9321-0.1224×106c, c is concentration in mol/L, peak current IpThe unit is mA, the linear correlation coefficient r = -0.9992, and the detection limit is 2.0 multiplied by 10-7mol/L；
The linear range of o-dihydroxybenzene was 2.0X 10-6～1.0×10-4mol/L, linear equation of Ip=-2.0763-0.0064×106c, c is concentration in mol/L, peak current IpThe unit is mA, the linear correlation coefficient r = -0.9998, and the detection limit is 2.0 multiplied by 10-7 mol/L；
The linear range of m-dihydroxybenzene is 5.0X 10-6～1.4×10-4mol/L, linear equation of Ip=-24.6716-0.0333×106c, c is concentration in mol/L, peak current IpThe unit is mA, the linear correlation coefficient r = -0.9995, and the detection limit is 5.0 multiplied by 10-7mol/L；
Combining the linear equation to determine the benzenediol isomer mixture solution sample with unknown concentration and calculate the concentration of each isomer; placing a three-component mixed solution of o-dihydroxybenzene, m-dihydroxybenzene and p-dihydroxybenzene with unknown concentration in an electrolytic cell, taking the electrode as the working electrode in claim 1, taking an Ag/AgCl electrode as a reference electrode, and taking a platinum electrode as a counter electrode; the experiment is carried out on a CHI842B electrochemical comprehensive tester, and the attached computer software is used for collecting and processing experimental data; differential pulse scanning is carried out in the potential range of-0.4-0.8V, and I of different isomers is respectively measured at different peak potentialsPA value; measuring the measured IPThe values are respectively substituted into the linear equation to calculate the adjacent valueThe respective concentrations of nitrophenol, m-nitrophenol and p-nitrophenol.
Claims (1)
1. By means of NH2-SBA15/CPE method for determining three isomers of benzenediol, characterized in that the method comprises the following steps:
firstly, a certain amount of o-dihydroxybenzene (CC), m-dihydroxybenzene (RC) and p-dihydroxybenzene (HQ) solution is accurately transferred into a phosphate buffer solution electrolytic cell containing 10mL of pH6.0 by a micropipette, and NH is added2SBA15/CPE as working electrode, Ag/AgCl electrode as reference electrode, and platinum electrode as counter electrode; the experiment was carried out on a CHI842B electrochemical comprehensive tester, with accompanying computer software for collecting experimental data and for determining the quality of the experimental dataProcessing; differential pulse scanning is carried out within the potential range of-0.4-0.8V, and a stable differential pulse voltammogram is recorded;
② the concentrations of o-dihydroxybenzene, m-dihydroxybenzene and p-dihydroxybenzene are respectively fixed at 2X 10-6Changing one of the concentrations by mol/L, and increasing the oxidation peak current along with the increase of the concentration to obtain a linear relation curve of the o-benzenediol, the m-benzenediol and the p-benzenediol; simultaneously, according to the determination principle of the relevant sensitivity, the detection limits of the three are determined;
the best conditions for measuring the isomers of the benzenediol are as follows: KH is selected as supporting electrolyte2PO4-Na2HPO4Solution buffer, optimal pH 6.0; the concentration of three isomers measured by a differential pulse method is in a good linear relation with peak current in a certain range;
the linear range of p-dihydroxybenzene was 1.0X 10-6～1.6×10-4mol/L, linear equation of Ip=-16.9321-0.1224×106c, c is concentration in mol/L, peak current IpThe unit is muA, the linear correlation coefficient r = -0.9992, and the detection limit is 2.0 multiplied by 10-7mol/L；
The linear range of o-dihydroxybenzene was 2.0X 10-6～1.0×10-4mol/L, linear equation of Ip=-2.0763-0.0064×106c, c is concentration in mol/L, peak current IpThe unit is muA, the linear correlation coefficient r = -0.9998, and the detection limit is 2.0 multiplied by 10-7 mol/L；
The linear range of m-dihydroxybenzene is 5.0X 10-6～1.4×10-4mol/L, linear equation of Ip=-24.6716-0.0333×106c, c is concentration in mol/L, peak current IpThe unit is muA, the linear correlation coefficient r = -0.9995, and the detection limit is 5.0 multiplied by 10-7mol/L；
Combining the linear equation to determine the benzenediol isomer mixture solution sample with unknown concentration and calculate the concentration of each isomer; placing a three-component mixed solution of o-dihydroxybenzene, m-dihydroxybenzene and p-dihydroxybenzene with unknown concentration in an electrolytic cell by using NH2SBA15/CPE as working electrode, Ag/AgClThe electrode is a reference electrode, and the platinum electrode is a counter electrode; the experiment is carried out on a CHI842B electrochemical comprehensive tester, and the attached computer software is used for collecting and processing experimental data; differential pulse scanning is carried out in the potential range of-0.4-0.8V, and I of different isomers is respectively measured at different peak potentialsPA value; measuring the measured IPThe values are respectively substituted into the linear equations obtained above to calculate the respective concentrations of the ortho-dihydroxybenzene, the meta-dihydroxybenzene and the para-dihydroxybenzene.
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| "Nanocomposite with Polypyrrole Encapsulated within SBA-15 Mesoporous Silica: Preparation and Its Electrochemical Application";Junping Dong等;《Electroanalysis》;20091231;第21卷(第16期);第1792-1798页 * |
| "硝基酚在MCM-41碳糊电极上的电化学行为";段烁等;《分析化学》;20091031;第37卷;第E053页 * |
| "纳米介孔材料的催化应用前景";闫继娜等;《无机材料学报》;20030731;第18卷(第4期);第728页第3段 * |
| Junping Dong等."Nanocomposite with Polypyrrole Encapsulated within SBA-15 Mesoporous Silica: Preparation and Its Electrochemical Application".《Electroanalysis》.2009,第21卷(第16期), |
| 段烁等."硝基酚在MCM-41碳糊电极上的电化学行为".《分析化学》.2009,第37卷 |
| 闫继娜等."纳米介孔材料的催化应用前景".《无机材料学报》.2003,第18卷(第4期), |
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