CN108956727B - Electrode modification material for simultaneously detecting hydroquinone and catechol in seawater - Google Patents

Electrode modification material for simultaneously detecting hydroquinone and catechol in seawater Download PDF

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CN108956727B
CN108956727B CN201810493831.5A CN201810493831A CN108956727B CN 108956727 B CN108956727 B CN 108956727B CN 201810493831 A CN201810493831 A CN 201810493831A CN 108956727 B CN108956727 B CN 108956727B
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陈灏
陈博扬
宋亚文
陈守刚
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Abstract

The invention relates to an electrochemical detection technology, in particular to a modified electrode for simultaneously detecting hydroquinone and pyrocatechol in seawater and a preparation and detection method of the electrode material. The preparation process comprises the following steps: surface modified MWCNTs and Co (Ac)2Adding absolute ethyl alcohol for ultrasonic treatment, slowly dripping ammonia water and stirring, transferring to a reaction kettle for hydrothermal reaction, cleaning and drying to obtain Co3O4/MWCNTs nano composite material. Co3O4The MWCNTs modified glassy carbon electrode realizes the simultaneous high-efficiency detection of catechol and hydroquinone under the alkalescent condition through differential pulse voltammetry. The detection range of the catechol is 10-700 mu M, the detection limit is 8.5 mu M, and the detection range of the hydroquinone is 10-800 mu MM, the detection limit is 5.6 mu M. Meanwhile, the electrode material realizes the simultaneous high-efficiency detection of catechol and hydroquinone in the actual seawater environment, has the advantages of good stability, wide detection range and good sensitivity and repeatability, and can be used for the high-efficiency determination of phenols in river water and seawater.

Description

Electrode modification material for simultaneously detecting hydroquinone and catechol in seawater
Technical Field
The invention relates to an electrochemical detection technology, in particular to a modified electrode for detecting hydroquinone and catechol in a seawater environment, a preparation method of the electrode and a detection method.
Background
The benzenediol is an important chemical raw material and is widely used in the aspects of cosmetics, tanning, pesticides, seasonings, pharmacy, synthetic dyes and the like in daily production and life. Hydroquinone (HQ) and catechol (CC) are isomers of two kinds of diphenols, which are commonly present in environmental samples as highly toxic environmental pollutants, and hydroquinone causes fatigue, headache and kidney damage, and catechol causes liver function to be decreased. As a priority pollutant of the american Environmental Protection Association (EPA) and the European Union (EU), HQ and CC are difficult to naturally degrade in natural ecological environment and have a great toxic effect on human beings and animals even at a low concentration. Therefore, achieving simultaneous detection of HQ and CC has been an important research topic for researchers in the field of analytical chemistry. Over the past few years, a wide variety of assays have been developed that can carry out the detection of both isomers, including high performance liquid chromatography, gas chromatography, spectrophotometry, fluorescence, and the like. Although these methods have high precision and sensitivity and can simultaneously detect a plurality of targets, most of the used instruments are expensive, the consumption of required reagents is high, the pretreatment of samples is complicated, and the operation of the instruments is complex.
In recent years, electrochemical sensing detection methods are popular among people because of simple and rapid detection operation, low detection cost, no complex sample pretreatment, high sensitivity and good selectivity. In the process of simultaneously detecting isomers of hydroquinone by electrochemistry, in order to obtain a stronger signal peak, glassy carbon electrodes are usually modified by a plurality of composite materials, such as noble metal nanoparticles, metal oxides, carbon nanomaterials, high-molecular polymers and the like.
Although the simultaneous detection of hydroquinone and catechol has been reported at present, most of them are performed under acidic or neutral conditions, such as patent 201310486179.1, 201410168270.3 and 201710563943.9, and the linear detection range is not wide enough, and few sensors suitable for detecting hydroquinone pollutants in alkaline environment are reported, because the seawater is weak alkaline, the pH value is generally between 7.0 and 8.5, and because of the strong interference of seawater, it is difficult to have suitable materials to realize high-efficiency detection under the condition of weak alkaline seawater. Therefore, the research and development of the electrode material which can be applied to the alkaline environment, particularly the actual seawater environment and can simultaneously detect the hydroquinone and the catechol has important research value.
Disclosure of Invention
The invention aims to solve the technical problem of providing a modified electrode capable of effectively detecting hydroquinone and pyrocatechol simultaneously in a seawater environment. The invention mixes Co3O4The nano material is compounded with the MWCNTs after surface modification, which can solve the problem of pure Co3O4The problem that the nano material is easy to agglomerate can also improve the conductivity of the nano material and enhance the detection sensitivity of the sensor. The material shows strong electrochemical sensing performance, can electrically catalyze and oxidize catechol and hydroquinone in a weak alkaline environment to generate oxidation currents with different peak potentials, and realizes the simultaneous and efficient detection of the hydroquinone and the catechol in the seawater. Wherein, the detection range of the catechol reaches 10-700 MuM, the detection limit reaches 8.5 MuM, the detection range of the hydroquinone reaches 10-800 MuM, and the detection limit reaches 5.6 MuM. Meanwhile, the electrode material in the actual seawater realizes the simultaneous high-efficiency detection of catechol and hydroquinone in the seawater environment. The modified electrode has good stability in seawater environment, wide detection range and good sensitivity and repeatability, and can be used for efficiently determining phenols in river water and seawater.
The technical problem to be solved by the invention is realized by the following technical scheme:
a modified electrode for detecting hydroquinone and pyrocatechol in sea water sample simultaneously, modified electrode is Co3O4the/MWCNTs nano composite material modified electrode.
The preparation method of the modified electrode comprises the following steps: firstly, MWCNTs and Co (Ac) after surface modification treatment2Adding into absolute ethyl alcohol for ultrasonic treatment, and then slowly dripping a certain amount of NH while stirring at room temperature3‧H2And O. Then transferring the mixed solution into a reaction kettle for hydrothermal reaction, and cleaning and drying a sample to obtain Co3O4MWCNTs nanocomposite, wherein Co has a diameter of 8-15nm3O4The particles are uniformly coated on the carbon nano tube to form a cable-shaped coating nano structure. Finally, the glassy carbon electrode is polished and cleaned, and Co with the concentration of 10mg/mL is prepared by using 0.5wt.% of CS acetic acid solution3O4And ultrasonically mixing the MWCNTs suspension uniformly, then spin-coating the mixture on a glassy carbon electrode, and freeze-drying to obtain the glassy carbon electrode. The method realizes the simultaneous and efficient detection of hydroquinone and catechol in the seawater under the condition of alkalescence (pH is about 7.5 and 8.2) by differential pulse voltammetry.
The Co3O4The preparation method of the MWCNTs nano composite material and the specific steps of the modified electrode are as follows:
(1) MWCNTs and Co (Ac) after surface modification treatment2Adding into absolute ethyl alcohol for ultrasonic treatment;
(2) then slowly dripping a certain amount of NH while stirring at room temperature3‧H2O; then transferring the mixed solution into a reaction kettle for hydrothermal reaction, and cleaning and drying a sample to obtain Co3O4MWCNTs nano composite material;
(3) polishing and cleaning the glassy carbon electrode, and preparing Co with the concentration of 10mg/mL by using 0.5wt.% of CS acetic acid solution3O4And ultrasonically mixing the MWCNTs suspension uniformly, then spin-coating the mixture on a glassy carbon electrode, and freeze-drying to obtain the glassy carbon electrode.
Said Co3O4The application of the MWCNTs nano composite material modified electrode realizes the simultaneous and efficient detection of hydroquinone and catechol in seawater under the condition of alkalescence (about 8.2 of pH) through differential pulse voltammetry.
Said Co3O4In the preparation method of the MWCNTs nano composite material modified electrode, the MWCNTs subjected to surface modification treatment are subjected to ultrasonic activation for 30min in 65% concentrated nitric acid solution, the modified carbon tube after separation is washed to be neutral by deionized water, and the modified carbon tube is placed in an oven to be dried at 80 ℃ after suction filtration.
Said Co3O4MWCNT and Co (Ac) with modified surface in preparation method of MWCNTs nanocomposite modified electrode2The mass ratio is 1: 1-1: 10.
said Co3O41/10 with ammonia water as solution is added in the preparation method of the MWCNTs nano composite material modified electrode, and the mixture is continuously stirred for 10 min.
Said Co3O4The preparation method of the MWCNTs nano composite material modified electrode is characterized in that the hydrothermal reaction temperature is 130-180 ℃, and the heat preservation reaction is carried out for 3 hours.
Said Co3O4The preparation method of the MWCNTs nano composite material modified electrode comprises the steps of cleaning, sequentially using absolute ethyl alcohol and ultrapure water for 3 times respectively, and then placing in a 60 ℃ drying oven to dry for 6 hours.
Drawings
FIG. 1, (a-c) Co3O4SEM image of/MWCNTs; (b, d) a TEM image; (f) the structure is schematic.
Figure 2, electrochemical behavior of HQ and CC at Co3O4/MWCNTs modified electrode surface in pH =7.5 and 8.2 environments.
FIG. 3(a) shows the DPV response curve recorded by continuously adding equal amounts of HQ and CC to the buffer solution, (b) shows the linear fit curve of the HQ response when HQ and CC are measured simultaneously; (c) the response of CC is linearly fitted to the curve.
FIG. 4 shows Co3O4The anti-interference performance of the MWCNTs sensor in the process of detecting HQ (a) and CC (b), (c) continuously testing 10 times of DPV response short-term stability, (d) repeatability and long-term stability within 4 weeks of storage.
FIG. 5 shows Co3O4The electrochemical sensor constructed by the MWCNTs is used for detecting and analyzing HQ and CC and recovering the sample.
Table 1 analysis of HQ and CC detection in actual seawater samples and sample recovery.
Detailed Description
The invention is further explained by the specific embodiment in the following with the attached drawings.
Example 1
Co3O4Preparation of MWCNTs composite nano material
First, surface modification treatment of MWCNTs is performed. Adding 0.5g of MWCNTs into 50mL of 65% concentrated nitric acid solution, carrying out ultrasonic treatment for 30min, then carrying out magnetic stirring on the mixture subjected to ultrasonic treatment for 12h at the oil bath temperature of 150 ℃, cooling and standing, carefully adding water, carrying out ultrasonic stirring for 15min, continuously standing, removing supernatant after layering, adding water, standing until no layering is formed, washing to be neutral by deionized water, carrying out suction filtration, and drying in an oven at 80 ℃ for 5 h.
20mg of surface-modified MWCNTs and 0.1g of Co (Ac)2‧4H2O2Adding into 25mL absolute ethyl alcohol for ultrasonic treatment for 20min, then slowly dropping 2.5mL ammonia water at room temperature under magnetic stirring of 400 rad/min. Then the mixed homogeneous solution is transferred to a 50mL polytetrafluoroethylene reaction kettle to be sealed and reacted for 3h under the environment of 160 ℃. Cooling to room temperature, centrifugally collecting reaction products, sequentially cleaning with anhydrous ethanol and ultrapure water for 3 times, and drying in an oven at 70 ℃ for 6 hours to obtain Co3O4the/MWCNTs composite nano material.
Co3O4The scanning pictures of the material compounded with the MWCNTs after surface treatment are shown in FIG. 1 (a-c), and it can be seen from the pictures that Co3O4The nano particles are uniformly modified on the outer wall of the MWCNTs material, and Co in the composite material3O4The diameter of the particles is 8-15 nm. Co can be seen from transmission electron microscopy pictures (FIG. 1 d, e)3O4the/MWCNTs composite nano material is in a nano cable state, the MWCNTs are used as core wires of the cable, and the outside of the MWCNTs is uniformly coated with a layer of Co3O4The nano layer composed of the nano particles and having the thickness of about 20nm forms a cable-shaped coating nano structure. On the nano-layer there are many layers made of Co3O4The porous structure formed by the accumulation of the nano particles is not only favorable for the diffusion of HQ and CC, but also increases the specific surface area of the material, and is favorable for catalytic detectionThe process was followed by the contact reaction. Co3O4The structure schematic diagram of the/MWCNTs composite nano material is shown in FIG. 1 f.
FIG. 2a shows MWCNTs material and Co3O4The XRD pattern of the/MWCNTs nano cable material has characteristic peaks of (002) and (100), and characteristic peaks of (111), (220), (311), (222), (400), (422), (511) and (440) in the composite material pattern belong to Co3O4The data is consistent with the JCDS card No. 43-1467 standard data, and no other miscellaneous peaks appear, which indicates that Co with high purity is directly obtained after simple hydrothermal reaction3O4the/MWCNTs composite nano material. Co3O4The infrared spectrum of the/MWCNTs composite nano material is shown in figure 2b, and is at 664cm-1And 575cm-1Two of the most obvious of (A) are Co3O4Vibration peak of medium metal-oxygen, 575cm-1The vibration peak of Co (III) -O at the octahedral position, and the stretching vibration peak of Co (II) -O at the tetrahedral position are at 664 cm-1. The vibration peaks at 1018cm-1 and 1568cm-1 belong to the C-C bond and C = C bond on MWCNTs, 2910cm-1The vibration peak belongs to a C-H bond in methylene, and the stretching vibration peak at 3397cm-1 belongs to an OH-vibration peak in water molecules adsorbed by a sample. The impedance spectrum may reveal changes in electron transport at the electrode interface caused by surface modification. FIG. 2c shows Co3O4/MWCNTs/GCE、Co3O4Impedance spectra of/GCE and bare electrode GCE. The diameter of the semi-circle of the charge transfer resistance of the electrode surface corresponding to the response of the spectrogram semi-circle region can represent the magnitude of the charge transfer resistance value of the electrode surface, as is apparent from fig. 2c, Co3O4The electrode impedance value of/MWCNTs/GCE is minimum, which shows that the composite addition of MWCNTs obviously improves and increases Co3O4The conductivity of the material.
Co3O4HQ and CC electrochemical pre-detection under/MWCNTs modified electrode
Firstly, a bare glassy carbon electrode (GCE, the diameter of 3 mm) is carefully polished by alumina powder with the grain sizes of 0.3 mu m and 0.05 mu m respectively, and then the polished GCE is subjected to ultrasonic cleaning by absolute ethyl alcohol and deionized water in sequenceAnd (6) processing. Co was formulated at a concentration of 10mg/mL using a 0.5wt.% CS acetic acid solution3O4And (3) uniformly ultrasonically shaking the MWCNTs suspension, dripping 10 mu L of the MWCNTs suspension onto a glassy carbon electrode, placing the glassy carbon electrode in a refrigerator at 4 ℃, and naturally drying the glassy carbon electrode for electrochemical detection. Electrochemical detection of 0.2M NaH at pH =7.5 and 8.22PO4-in CA solution.
Fig. 3 shows the electrochemical behavior of HQ and CC on the surface of the modified electrode obtained by DPV testing. FIG. 3 a shows that the presence of HQ alone in a solution of pH7.5 produces an HQ oxidation peak at 0.076V, the presence of CC alone produces a CC oxidation peak at 0.176V, and the presence of HQ and CC produces two oxidation peaks, respectively, with no difference in intensity and position from HQ and CC alone, indicating that Co is present3O4The MWCNTs modified electrode can realize simultaneous detection of HQ and CC. FIG. 3b is a pre-test of HQ and CC at pH8.2, which resulted in two oxidation peak signals at 0.03V and 0.14V when both HQ and CC were present in solution, with oxidation peak intensities significantly greater than those at pH7.0, indicating that Co was present3O4The MWCNTs modified electrode can realize simultaneous detection of HQ and CC in a weak alkaline environment, and seawater is weak alkaline water, so that simultaneous detection of HQ and CC in seawater is hopefully realized. FIG. 3c, d are DPV response curves of HQ and CC under different modified electrodes. As can be seen from the figure, the Co after recombination3O4The detection response signals (115, 103 muA) of the/MWCNTs modified electrode pair HQ and CC are 34 times and 31 times of the signals (3.35, 3.3 muA) generated by Co3O4 modified electrode alone, and 4 times and 3 times of the signals (28.8, 35.2 muA) generated by MWCNTs modified electrode alone. Thus, mixing Co3O4The material compounded with MWCNTs can be applied to simultaneous detection of HQ and CC under the condition of weak base, and the detection sensitivity of the sensor is greatly improved.
FIG. 4 shows that HQ and CC are continuously added to the solution to be tested at the same time at the same concentration (5-900. mu.M), the oxidation potentials of the HQ and the CC are not changed, the oxidation current increases with the increase of the concentration, and the response linear fitting equation is as follows: HQ: y1(μ a) =8.979+0.569x (R =0.996, — (v))<x<200μM)，y2(μA)=69.0+0.189x(R=0.993,200<x<800μM)。CC：y1(μA)=-0.1+0.53x(R=0.999,~<x<200μM)，y2(μA)=43.66+0.30x(R=0.999,200<x<700 μ M). The lowest detection limits were 5.6. mu.M and 8.5. mu.M, respectively. This can be attributed primarily to Co3O4The high-efficiency catalytic effect of the nano material in an alkaline environment and the catalytic adsorption capacity of the MWCNTs to HQ and CC.
And (3) testing the capability of the sensing electrode to resist interference in an actual sample and stability. Co shown in FIG. 53O4The electrochemical sensor constructed by the MWCNTs has the detection anti-interference performance on HQ and CC, and a method of additionally adding interfering substances possibly existing in an actual sample into a solution with known HQ and CC concentrations is adopted. In the DPV detection of FIGS. 5a, b, 100 times of NaCl, KCl, KBr, oxalic acid, Na was added to 100. mu.M of the diphenol isomer2SO4，(NH4)2SO4，C3H3NaO3Citric acid, NH4NO3And the influence of 50 times of resorcinol and phenol on detection signals of HQ and CC is less than 6%, which shows that the electrochemical sensor has strong anti-interference capability. To detect Co3O4The stability and performance reproducibility of the MWCNTs constructed sensor are respectively tested as follows. As shown in fig. 5c, after 10 consecutive DPV scans in the test solution containing both HQ and CC, the initial electrochemical signal was almost unchanged with relative standard deviations of 1.98% and 4.21%, respectively, indicating that the sensor has excellent short-term stability in the detection of HQ and CC. Meanwhile, after continuous testing for four weeks (fig. 5 d), the detection sensitivity to HQ still reaches more than 91.5% of the initial value, and the detection sensitivity to CC, although being reduced relative to the HQ performance, can also reach more than 72.1% of the initial value, which indicates that the sensor has good reproducibility and long-term stability.
Actual seawater test analysis
To further verify Co3O4The MWCNTs are used for constructing the practical applicability of the electrochemical sensor, the concentrations of HQ and CC are tested and analyzed by adopting a standard addition method, and the results are shown in Table 1. Taking three parallel samples from each group of samples for testing, except forThe standard deviation of HQ in the sample 2 is 13%, and the other standard deviations are lower than 6.3%, which shows that the detection results of the HQ and CC electrochemical detection sensor in the actual seawater sample can be accepted, the sample recovery rate is calculated by the formula that the recovery rate (%) = (total amount-detection amount)/the addition amount of × 100%, the HQ recovery rate is 96.4% -109.1% in total and the CC recovery rate is 97.5% -104.2%, which shows that the electrochemical detection sensor is accurate, simple and convenient, and has the capability of simultaneously analyzing and detecting HQ and CC pollutants in the actual seawater sample.
TABLE 1 HQ and CC detection analysis in actual seawater samples and sample recovery
Figure RE-DEST_PATH_IMAGE001

Claims (9)

1. Co3O4The MWCNTs nano composite material modified electrode is characterized in that:
(1) MWCNTs and Co (Ac) after surface modification treatment2Adding into absolute ethyl alcohol for ultrasonic treatment;
(2) then slowly adding NH dropwise while stirring at room temperature3·H2O; then transferring the mixed solution into a reaction kettle for hydrothermal reaction, and cleaning and drying a sample to obtain Co3O4MWCNTs nano composite material;
(3) polishing and cleaning the glassy carbon electrode, and preparing Co with the concentration of 10mg/mL by using 0.5wt.% of CS acetic acid solution3O4And ultrasonically mixing the MWCNTs suspension uniformly, then spin-coating the mixture on a glassy carbon electrode, and freeze-drying to obtain the glassy carbon electrode.
2. Co according to claim 13O4The MWCNTs nano composite material modified electrode is characterized in that: the Co3O4In the/MWCNTs nano composite material, Co3O4The diameter of the particles is 8-15nm, Co3O4The particles are uniformly coated on the carbon nano tube.
3. Co according to claim 13O4The MWCNTs nano composite material modified electrode is characterized in that: the MWCNTs subjected to surface modification treatment in the step (1) are subjected to ultrasonic activation for 30min by using a 65% concentrated nitric acid solution, the modified carbon tubes are separated and washed by deionized water to be neutral, and the modified carbon tubes are subjected to suction filtration and then are placed in an oven to be dried at 80 ℃.
4. Co according to claim 13O4The MWCNTs nano composite material modified electrode is characterized in that: MWCNT and Co (Ac) after surface modification in step (1)2The mass ratio is 1: 1-1: 10.
5. co according to claim 13O4The MWCNTs nano composite material modified electrode is characterized in that: 1/10 (the volume of ammonia water is equal to the volume of the solution) is added in the step (2), and the stirring is continued for 10 min.
6. Co according to claim 13O4The MWCNTs nano composite material modified electrode is characterized in that: the hydrothermal reaction temperature in the step (2) is 130-180 ℃, and the reaction is carried out for 3 hours under the condition of heat preservation.
7. Co according to claim 13O4The MWCNTs nano composite material modified electrode is characterized in that: and (3) cleaning in the step (2), sequentially using absolute ethyl alcohol and ultrapure water for 3 times respectively, and then drying in an oven at 60 ℃ for 6 hours.
8. Co according to any one of claims 1 to 73O4The application of the MWCNTs nano composite material modified electrode in simultaneously detecting hydroquinone and catechol in seawater.
9. The application of claim 8 in simultaneous detection of hydroquinone and catechol in seawater, wherein: the simultaneous detection of hydroquinone and catechol in seawater at pH 7.0-8.5 is realized by differential pulse voltammetry.
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