CN105223260B - Electrochemical sensor of trace quick detection butyl p-hydroxybenzoate and preparation method thereof - Google Patents
Electrochemical sensor of trace quick detection butyl p-hydroxybenzoate and preparation method thereof Download PDFInfo
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- CN105223260B CN105223260B CN201510679180.5A CN201510679180A CN105223260B CN 105223260 B CN105223260 B CN 105223260B CN 201510679180 A CN201510679180 A CN 201510679180A CN 105223260 B CN105223260 B CN 105223260B
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Abstract
The present invention relates to electrochemical sensor and Electroanalytical Chemistry field, specifically disclose a kind of electrochemical sensor of trace quick detection preservative butyl p-hydroxybenzoate and preparation method thereof, measure high sensitivity of the electrochemical sensor to preservative butyl p-hydroxybenzoate, selectivity is good, it is simple to operate, cost is cheap, credible result.Electrochemical sensor of the present invention includes working electrode, reference electrode, to electrode；Described working electrode is that surface drop coating has electroactive very high hollow CeO2The glass-carbon electrode of microballoon modified membrane.Electrochemical sensor prepared by the present invention has been successfully applied to the detection of spiced dried beancurd, multiple fiber element complex capsule, jam, butyl p-hydroxybenzoate in cosmetics.
Description
Technical field
The present invention relates to electrochemical sensor and Electroanalytical Chemistry field, particularly for detection cosmetics, food and doctor
Trace quick detection electrochemical sensor of butyl p-hydroxybenzoate and preparation method thereof in medicine.
Background technology
Butyl p-hydroxybenzoate is also known as nipagin esters, be purposes is most wide in the world at present, dosage is maximum, applying frequency most
High a series of anticorrosion agent, had a wide range of application based on its efficient, non-volatile, pH, good sterilizing ability, easy compatibility and chemistry
Stability is good and is widely used in daily use chemicals, cosmetics, medicine, food, feed and various industrial antisepsis aspect.In recent years, with
The development of social economy, the dosage of paraben preservative gradually increase, and residual quantity increasingly increases in the environment.By
Relatively strong in the acidity and corrosivity of butyl p-hydroxybenzoate, the people of hyperhydrochloria and unsuitable for children eat and contain such anti-corrosion
The food of agent；Routledge etc. also has found that p-hydroxybenzoate has weak estrogen active first, and this discovery is to original
The viewpoint of " p-hydroxybenzoate hypotoxicity " proposes challenge.Therefore we need a set of efficiency high, selectivity strong to hydroxyl
The detection method of yl benzoic acid butyl ester, it can provide important information foundation for reasonable employment preservative.
CeO2It is a kind of important rare earth oxide, because it has special construction and pattern, increasingly causes people very big
Ground research interest, it is widely used in the fields such as medical science, material, chemistry, biology and environmental project.Wherein, hollow nanosphere because
There is low-density, high-specific surface area, high surface and Surface Permeability, in drug conveying carrier, light filler, people
Making the fields such as cell, chemical sensor and catalysis and absorption has extremely wide application prospect.
At present, the assay method of butyl p-hydroxybenzoate mainly has high performance liquid chromatography, high performance liquid chromatography-matter
Spectrometry, thin-layered chromatography, capillary electrophoresis, gas chromatography etc..However, these methods or sample pre-treatments step to be present numerous
The not high weakness of trivial, sensitivity, or need to use the instrument of complex and expensive, it is necessary to professional is operated, or cumbersome,
It is time-consuming, sensitivity and poor selectivity, it tends to be difficult to carry out trace detection.
Electrochemical method have fast response time, it is easy to operate, inexpensive, time saving, durable, can carry, high sensitivity, selection
Property it is good, with Modern Analytical Instrument compatibility it is good and can real-time online detect the features such as, increasingly cause the concern of researcher.
There is not been reported for electrochemical determination method about butyl p-hydroxybenzoate in cosmetics, food and medicine, therefore
It is one to provide a kind of detection to preservative butyl p-hydroxybenzoate to have superior sensitivity and the electrochemical sensor of selectivity
The work of individual worth research.Based on this, the present invention establishes electrochemical method trace quick detection in cosmetics, food and medicine
The sensor of butyl p-hydroxybenzoate.
The content of the invention
In order to overcome the detection to preservative butyl p-hydroxybenzoate in the prior art to be completed by expensive instrument,
And the defects of detecting step complexity, the invention provides one kind to be based on hollow CeO2The trace quick detection preservative of microballoon is to hydroxyl
Electrochemical sensor of yl benzoic acid butyl ester and preparation method thereof.The object of the present invention is achieved like this：
The electrochemical sensor of trace quick detection preservative butyl p-hydroxybenzoate, including working electrode, reference electricity
Pole, to electrode；It is characterized in that：Described working electrode is that surface drop coating has the electroactive very high hollow CeO in surface2Microballoon is repaiied
Adorn the glass-carbon electrode of film；
The preparation method of the electrochemical sensor of described trace quick detection preservative butyl p-hydroxybenzoate, including
Following steps：
Step 1: the synthesis of Ce-Cit coordination polymer hollow microspheres：
6 mmol citric acid is added in 24 mL secondary waters, 2 mmol Ce (NO3)3·6H2O is added under agitation
In above-mentioned citric acid solution, after stirring a few minutes, transfer the solution into 30 mL reactors, seal, 160 °C of 12 h of reaction,
PH value is adjusted with 1mol/L HCl, reactant quality is adjusted when necessary, obtained product is washed several times respectively with water and ethanol,
60 °C of dryings；
Step 2: hollow CeO2The synthesis of microballoon：The Ce-Cit coordination polymer hollow microspheres that step 1 ancestor synthesizes are existed
365 °C of 1.5 h of calcining obtain object；
Step 3: hollow CeO2The scattered pretreatment of microballoon：
Weigh obtained hollow CeO in step 22Microsphere powder, adds secondary water, and 2 h of ultrasound obtain mass concentration as 2
Mg/mL dispersion liquid, for drop coating modified electrode；
Step 4: the pretreatment of glass-carbon electrode：
The removal of impurities process can be carried out or in order to simplify the step of cleaning process according to the conventional method of this area, preferably
Removal of impurities process concretely comprises the following steps：Glass-carbon electrode is polished with the aluminum oxide polishing powder of 0.3 μm and 0.05 μm respectively, passed through
After water rinses, then it is 1 to use volume ratio successively:1 salpeter solution, ethanol solution and secondary water is cleaned by ultrasonic 1 min；
Step 5: the preparation of electrochemical sensor：
The hollow CeO that will be obtained in step 32Microballoon dispersant liquid drop is coated onto the pretreated glassy carbon electrode surface of step 4,
The electrochemical sensor of preservative butyl p-hydroxybenzoate is obtained after evaporation drying；
Further, the electrochemical property test of routine has been carried out to above-mentioned modified electrode, as a result well；
The electrochemical sensor of the trace quick detection preservative butyl p-hydroxybenzoate can be applied to measure and make up
The concentration of butyl p-hydroxybenzoate in product, food and medicine, sensitivity, the degree of accuracy, precision and selectivity are good；
Described sample includes spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetics；
Described specific testing conditions are：
Determine medium：0.1 mol/L H2SO4；
Detect current potential：1.1 V；
Accumulating potential：0.8 V
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
Described specific detection method is：30 μ L 0.01mol/L butyl p-hydroxybenzoate standard liquid is taken to 3
In mL measure media, after stirring, cyclic voltammetry curve is gathered；Take 15 μ L 0.001mol/L butyl p-hydroxybenzoate
Standard liquid is determined in medium to 3 mL, after stirring, is enriched with 1 min, is gathered differentiated pulse volt-ampere curve；In 1.1 V electricity
Under position, stirring 1 min of enrichment, differentiated pulse volt of the collection various concentrations butyl p-hydroxybenzoate on the electrochemical sensor
Pacify curve；With 5.0 mmol/L K3[Fe(CN)6]/K4[Fe(CN)6]（1:1）For probe, in 0.l mol/L PBS（pH =
7.0）In 0.l mol/L KCl solution, to obtained hollow CeO2Microballoon modified glassy carbon electrode carries out electrochemical ac resistance
Anti- spectrum（EIS）Characterize；Weigh respectively spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetic sample respectively about 1.0 g in
In 50 mL conical flasks, 15 mL methanol are added, the min of ultrasonic extraction 10 is mixed, takes about 10 mL solution in centrifuge tube, with
10000 r/min centrifuge 10 min, and supernatant liquor filters through 0. 45 μm of organic phase filter membranes, then takes 100 μ L accordingly to carry respectively
Take liquid to add in 3 mL measure media to be tested and analyzed.
Positive beneficial effect：The invention has the advantages that：（1）The present invention is with hollow CeO2Microballoon is as sensor sensing
Material, simplicity is prepared, cost is cheap, has the advantages of specific surface area is big, good conductivity and accumulation ability are strong, and drip using simple
Apply and the method for evaporation solvent can form uniform film in electrode surface, preparation process only needs 4 min；Prepared material is not
It is small on the influence of operator's health containing material poisonous, pollution environment, being harmful to human body, it is environmentally friendly；(2)
The electrochemical response signal of butyl p-hydroxybenzoate can be significantly improved, sensitivity for analysis is high, butyl p-hydroxybenzoate
Detection limit is up to 4.15 × 10-8 mol/L；(3) analyze speed is fast, can directly determine, and the analysis time of whole sample is about 5
Min, can meet the needs of live fast slowdown monitoring；(4) favorable reproducibility, determined with 20 sensors in the sample of comparable sodium to hydroxyl
During yl benzoic acid butyl ester, relative standard deviation（RSD）Less than 2.5%；(5) it is easy to operate, it is not necessary to special experiment condition, to be easy to
Carry, it is practical：By the sensor application in the measure of spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetics etc.
In, tested by mark-on, find recovery of standard addition between 98.2%-107%, acquired results are with using high performance liquid chromatography
Eligible result is basically identical, illustrates that sensor degree of accuracy in the measure of actual sample is good.Present invention also offers according to above-mentioned
Preparation method prepared by electrochemical sensor and the electrochemical sensor in butyl p-hydroxybenzoate is detected should
With.
Brief description of the drawings
Fig. 1 is hollow CeO2The structural representation of microballoon modified glassy carbon electrode：
Fig. 2 is hollow CeO2The scanning electron microscope diagram of microballoon；
Fig. 3 is butyl p-hydroxybenzoate in (a) bare glassy carbon electrode and (b) hollow CeO2Circulation on microballoon modified electrode
Volt-ampere curve；
Fig. 4 butyl p-hydroxybenzoates are in (a) bare glassy carbon electrode and (b) hollow CeO2Differential arteries and veins on microballoon modified electrode
Rush volt-ampere curve;
Fig. 5 is differentiated pulse volt-ampere curve of the various concentrations butyl p-hydroxybenzoate on the electrochemical sensor；Insert
Figure is the range of linearity for detecting butyl p-hydroxybenzoate；
Fig. 6 is (a) bare glassy carbon electrode and (b) hollow CeO2The AC impedance figure of microballoon modified electrode；
It is in figure：Hollow CeO2Modified membrane 1, glass carbon substrate 2, insulating barrier 3, the contact conductor 4 of microballoon.
Embodiment
With reference to embodiment, the present invention is described further：
The preparation method of the electrochemical sensor of described trace quick detection preservative butyl p-hydroxybenzoate, including
Following steps：
Step 1: the synthesis of Ce-Cit coordination polymer hollow microspheres：
6 mmol citric acid is added in 24 mL secondary waters, 2 mmol Ce (NO3)3·6H2O is added under agitation
In above-mentioned citric acid solution, after stirring a few minutes, transfer the solution into 30 mL reactors, seal, 160 °C of 12 h of reaction,
PH value is adjusted with 1mol/L HCl, reactant quality is adjusted when necessary, obtained product is washed several times respectively with water and ethanol,
60 °C of dryings；
Step 2: hollow CeO2The synthesis of microballoon：The Ce-Cit coordination polymer hollow microspheres that step 1 ancestor synthesizes are existed
365 °C of 1.5 h of calcining obtain object；
Step 3: hollow CeO2The scattered pretreatment of microballoon：
Weigh obtained hollow CeO in step 22Microsphere powder, adds secondary water, and 2 h of ultrasound obtain mass concentration as 2
Mg/mL dispersion liquid, for drop coating modified electrode；
Step 4: the pretreatment of glass-carbon electrode：
The removal of impurities process can be carried out or in order to simplify the step of cleaning process according to the conventional method of this area, preferably
Removal of impurities process concretely comprises the following steps：Glass-carbon electrode is polished with the aluminum oxide polishing powder of 0.3 μm and 0.05 μm respectively, passed through
After water rinses, then it is 1 to use volume ratio successively:1 salpeter solution, ethanol solution and secondary water is cleaned by ultrasonic 1 min；
Step 5: the preparation of electrochemical sensor：
The hollow CeO that will be obtained in step 32Microballoon dispersant liquid drop is coated onto the pretreated glassy carbon electrode surface of step 4,
The electrochemical sensor of preservative butyl p-hydroxybenzoate is obtained after evaporation drying；
Further, the electrochemical property test of routine has been carried out to above-mentioned modified electrode, as a result well；
The electrochemical sensor of the trace quick detection preservative butyl p-hydroxybenzoate can be applied to measure and make up
The concentration of butyl p-hydroxybenzoate in product, food and medicine, sensitivity, the degree of accuracy, precision and selectivity are good；
Described sample includes spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetics；
Described specific testing conditions are：
Determine medium：0.1 mol/L H2SO4；
Detect current potential：1.1 V；
Accumulating potential：0.8 V
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
Described specific detection method is：30 μ L 0.01mol/L butyl p-hydroxybenzoate standard liquid is taken to 3
In mL measure media, after stirring, cyclic voltammetry curve is gathered；Take 15 μ L 0.001mol/L butyl p-hydroxybenzoate
Standard liquid is determined in medium to 3 mL, after stirring, is enriched with 1 min, is gathered differentiated pulse volt-ampere curve；In 1.1 V electricity
Under position, stirring 1 min of enrichment, differentiated pulse volt of the collection various concentrations butyl p-hydroxybenzoate on the electrochemical sensor
Pacify curve；With 5.0 mmol/L K3[Fe(CN)6]/K4[Fe(CN)6]（1:1）For probe, in 0.l mol/L PBS（pH =
7.0）In 0.l mol/L KCl solution, to obtained hollow CeO2Microballoon modified glassy carbon electrode carries out electrochemical ac resistance
Anti- spectrum（EIS）Characterize；Weigh respectively spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetic sample respectively about 1.0 g in
In 50 mL conical flasks, 15 mL methanol are added, the min of ultrasonic extraction 10 is mixed, takes about 10 mL solution in centrifuge tube, with
10000 r/min centrifuge 10 min, and supernatant liquor filters through 0. 45 μm of organic phase filter membranes, then takes 100 μ L accordingly to carry respectively
Take liquid to add in 3 mL measure media to be tested and analyzed.
Embodiment 1
The electrochemical sensor of trace quick detection preservative butyl p-hydroxybenzoate, including working electrode, reference electricity
Pole, to electrode；It is characterized in that：Described working electrode is that surface drop coating has electroactive very high hollow CeO2Microballoon modified membrane
Glass-carbon electrode, as shown in figure 1,1 be the surface drop coating of glass carbon substrate 2 have hollow CeO2The modified membrane of microballoon, 2 be glass carbon substrate, 3
For insulating barrier, 4 contact conductor to be connected with glass carbon substrate 2；
The preparation method of the electrochemical sensor of described trace quick detection preservative butyl p-hydroxybenzoate, including
Following steps：
Step 1：The synthesis of Ce-Cit coordination polymer hollow microspheres：
6 mmol citric acid is added in 24 mL secondary waters, 2 mmol Ce (NO3)3·6H2O is added under agitation
In above-mentioned citric acid solution, after stirring a few minutes, transfer the solution into 30 mL reactors, seal, 160 °C of 12 h of reaction,
PH value is adjusted with 1mol/L HCl, reactant quality is adjusted when necessary, obtained product is washed several times respectively with water and ethanol,
60 °C of dryings.
Step 2：Hollow CeO2The synthesis of microballoon：Ce-Cit coordination polymers hollow microsphere is calcined into 1.0 h at 365 °C
Obtain object；
Step 3：Hollow CeO2The scattered pretreatment of microballoon：
Weigh obtained hollow CeO in step step 22Microsphere powder, adds secondary water, and 2 h of ultrasound obtain mass concentration
For 2 mg/mL dispersion liquid, for drop coating modified electrode；
Step 4：The pretreatment of glass-carbon electrode：
The removal of impurities process can be carried out or in order to simplify the step of cleaning process according to the conventional method of this area, preferably
Removal of impurities process concretely comprises the following steps：Glass-carbon electrode is polished with the aluminum oxide polishing powder of 0.3 μm and 0.05 μm respectively, passed through
After water rinses, then it is 1 to use volume ratio successively:1 salpeter solution, ethanol solution and secondary water is cleaned by ultrasonic 1 min；
Step 5：The preparation of electrochemical sensor：
The hollow CeO that will be obtained in step step 32Microballoon dispersant liquid drop is coated onto the pretreated glass carbon of step step 4
Electrode surface, the electrochemical sensor of new food preservative butyl p-hydroxybenzoate is obtained after evaporation drying；
Further, the electrochemical property test of routine has been carried out to above-mentioned modified electrode, as a result well；
The electrochemical sensor of the trace quick detection preservative butyl p-hydroxybenzoate can be applied to measure and make up
The concentration of butyl p-hydroxybenzoate in product, food and medicine, sensitivity, the degree of accuracy, precision and selectivity are good；
Described sample includes spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetics；
Described specific testing conditions are：
Determine medium：0.1 mol/L H2SO4；
Detect current potential：1.1 V；
Accumulating potential：0.8 V
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
Described specific detection method is：30 μ L 0.01mol/L butyl p-hydroxybenzoate standard liquid is taken to 3
In mL measure media, after stirring, cyclic voltammetry curve is gathered；Take 15 μ L 0.001mol/L butyl p-hydroxybenzoate
Standard liquid is determined in medium to 3 mL, after stirring, is enriched with 1 min, is gathered differentiated pulse volt-ampere curve；In 1.1 V electricity
Under position, stirring 1 min of enrichment, differentiated pulse volt of the collection various concentrations butyl p-hydroxybenzoate on the electrochemical sensor
Pacify curve；With 5.0 mmol/L K3[Fe(CN)6]/K4[Fe(CN)6]（1:1）For probe, in 0.l mol/L PBS（pH =
7.0）In 0.l mol/L KCl solution, to obtained hollow CeO2Microballoon modified glassy carbon electrode carries out electrochemical ac resistance
Anti- spectrum（EIS）Characterize；Weigh respectively spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetic sample respectively about 1.0 g in
In 50 mL conical flasks, 15 mL methanol are added, the min of ultrasonic extraction 10 is mixed, takes about 10 mL solution in centrifuge tube, with
10000 r/min centrifuge 10 min, and supernatant liquor filters through 0. 45 μm of organic phase filter membranes, then takes 100 μ L accordingly to carry respectively
Take liquid to add in 3 mL measure media to be tested and analyzed.
Embodiment 2
The electrochemical sensor of trace quick detection preservative butyl p-hydroxybenzoate, including working electrode, reference electricity
Pole, to electrode；It is characterized in that：Described working electrode is that surface drop coating has electroactive very high hollow CeO2Microballoon modified membrane
Glass-carbon electrode, as shown in figure 1,1 be the surface drop coating of glass carbon substrate 2 have hollow CeO2The modified membrane of microballoon, 2 be glass carbon substrate, 3
For insulating barrier, 4 contact conductor to be connected with glass carbon substrate 2；
The preparation method of the electrochemical sensor of described trace quick detection preservative butyl p-hydroxybenzoate, including
Following steps：
Step 1：The synthesis of Ce-Cit coordination polymer hollow microspheres：
6 mmol citric acid is added in 24 mL secondary waters, 2 mmol Ce (NO3)3·6H2O is added under agitation
In above-mentioned citric acid solution, after stirring a few minutes, transfer the solution into 30 mL reactors, seal, 160 °C of 12 h of reaction,
PH value is adjusted with 1mol/L HCl, reactant quality is adjusted when necessary, obtained product is washed several times respectively with water and ethanol,
60 °C of dryings；
Step 2：Hollow CeO2The synthesis of microballoon：Ce-Cit coordination polymers hollow microsphere is calcined into 1.5 h at 365 °C
Object is obtained, the SEM of the material is as shown in Figure 2.
Step 3：Hollow CeO2The scattered pretreatment of microballoon：
Weigh obtained hollow CeO in step step 22Microsphere powder, adds secondary water, and 2 h of ultrasound obtain mass concentration
For 2 mg/mL dispersion liquid, for drop coating modified electrode；
Step 4：The pretreatment of glass-carbon electrode：
The removal of impurities process can be carried out or in order to simplify the step of cleaning process according to the conventional method of this area, preferably
Removal of impurities process concretely comprises the following steps：Glass-carbon electrode is polished with the aluminum oxide polishing powder of 0.3 μm and 0.05 μm respectively, passed through
After water rinses, then it is 1 to use volume ratio successively:1 salpeter solution, ethanol solution and secondary water is cleaned by ultrasonic 1 min；
Step 5：The preparation of electrochemical sensor：
The hollow CeO that will be obtained in step step 32Microballoon dispersant liquid drop is coated onto the pretreated glass carbon of step step 4
Electrode surface, the electrochemical sensor of new food preservative butyl p-hydroxybenzoate is obtained after evaporation drying；
Further, the electrochemical property test of routine has been carried out to above-mentioned modified electrode, as a result well；
The electrochemical sensor of the trace quick detection preservative butyl p-hydroxybenzoate can be applied to measure and make up
The concentration of butyl p-hydroxybenzoate in product, food and medicine, sensitivity, the degree of accuracy, precision and selectivity are good；
Described sample includes spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetics；
Described specific testing conditions are：
Determine medium：0.1 mol/L H2SO4；
Detect current potential：1.1 V；
Accumulating potential：0.8 V
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
Described specific detection method is：30 μ L 0.01mol/L butyl p-hydroxybenzoate standard liquid is taken to 3
In mL measure media, after stirring, cyclic voltammetry curve is gathered, as a result as shown in Figure 3；Take 15 μ L 0.001mol/L pair
Butoben standard liquid is determined in medium to 3 mL, after stirring, is enriched with 1 min, is gathered differentiated pulse volt-ampere
Curve, as shown in Figure 4；Under 1.1 V current potentials, stirring 1 min of enrichment, collection various concentrations butyl p-hydroxybenzoate is in the electricity
Differentiated pulse volt-ampere curve on chemical sensor, as a result as shown in Figure 5；With 5.0 mmol/L K3[Fe(CN)6]/K4[Fe
(CN)6]（1:1）For probe, in 0.l mol/L PBS（pH = 7.0）In 0.l mol/L KCl solution, in obtained
Empty CeO2Microballoon modified glassy carbon electrode carries out electrochemical alternate impedance spectrum（EIS）Characterize, as a result as shown in Figure 6；Five are weighed respectively
Respectively about 1.0 g in 50 mL conical flasks, add 15 mL first for fragrant dried bean curd, multiple fiber element complex capsule, jam, cosmetic sample
Alcohol, the min of ultrasonic extraction 10 is mixed, takes about 10 mL solution in centrifuge tube, centrifuge 10 min with 10000 r/min, upper strata is clear
Liquid filters through 0. 45 μm of organic phase filter membranes, then takes the corresponding extract solutions of 100 μ L to add in 3 mL measure media respectively and is examined
Analysis is surveyed, the results are shown in Table 1, table 2.
Embodiment 3
The electrochemical sensor of trace quick detection preservative butyl p-hydroxybenzoate, including working electrode, reference electricity
Pole, to electrode；It is characterized in that：Described working electrode is that surface drop coating has electroactive very high hollow CeO2Microballoon modified membrane
Glass-carbon electrode, as shown in figure 1,1 be the surface drop coating of glass carbon substrate 2 have hollow CeO2The modified membrane of microballoon, 2 be glass carbon substrate, 3
For insulating barrier, 4 contact conductor to be connected with glass carbon substrate 2；
The preparation method of the electrochemical sensor of described trace quick detection preservative butyl p-hydroxybenzoate, including
Following steps：
Step 1：The synthesis of Ce-Cit coordination polymer hollow microspheres：
6 mmol citric acid is added in 24 mL secondary waters, 2 mmol Ce (NO3)3·6H2O is added under agitation
In above-mentioned citric acid solution, after stirring a few minutes, transfer the solution into 30 mL reactors, seal, 160 °C of 12 h of reaction,
PH value is adjusted with 1mol/L HCl, reactant quality is adjusted when necessary.Obtained product is washed several times respectively with water and ethanol,
60 °C of dryings；
Step 2：Hollow CeO2The synthesis of microballoon：Ce-Cit coordination polymers hollow microsphere is calcined into 2.0 h at 365 °C
Obtain object；
Step 3：Hollow CeO2The scattered pretreatment of microballoon：
Weigh obtained hollow CeO in step step 22Microsphere powder, adds secondary water, and 2 h of ultrasound obtain mass concentration
For 2 mg/mL dispersion liquid, for drop coating modified electrode；
Step 4：The pretreatment of glass-carbon electrode：
The removal of impurities process can be carried out or in order to simplify the step of cleaning process according to the conventional method of this area, preferably
Removal of impurities process concretely comprises the following steps：Glass-carbon electrode is polished with the aluminum oxide polishing powder of 0.3 μm and 0.05 μm respectively, passed through
After water rinses, then it is 1 to use volume ratio successively:1 salpeter solution, ethanol solution and secondary water is cleaned by ultrasonic 1 min；
Step 5：The preparation of electrochemical sensor：
The hollow CeO that will be obtained in step step 32Microballoon dispersant liquid drop is coated onto the pretreated glass carbon of step step 4
Electrode surface, the electrochemical sensor of new food preservative butyl p-hydroxybenzoate is obtained after evaporation drying；
Further, the electrochemical property test of routine has been carried out to above-mentioned modified electrode, as a result well；
The electrochemical sensor of the trace quick detection preservative butyl p-hydroxybenzoate can be applied to measure and make up
The concentration of butyl p-hydroxybenzoate in product, food and medicine, sensitivity, the degree of accuracy, precision and selectivity are good；
Described sample includes spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetics；
Described specific testing conditions are：
Determine medium：0.1 mol/L H2SO4；
Detect current potential：1.1 V；
Accumulating potential：0.8 V
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
Described specific detection method is：30 μ L 0.01mol/L butyl p-hydroxybenzoate standard liquid is taken to 3
In mL measure media, after stirring, cyclic voltammetry curve is gathered；Take 15 μ L 0.001mol/L butyl p-hydroxybenzoate
Standard liquid is determined in medium to 3 mL, after stirring, is enriched with 1 min, is gathered differentiated pulse volt-ampere curve；In 1.1 V electricity
Under position, stirring 1 min of enrichment, differentiated pulse volt of the collection various concentrations butyl p-hydroxybenzoate on the electrochemical sensor
Pacify curve；With 5.0 mmol/L K3[Fe(CN)6]/K4[Fe(CN)6]（1:1）For probe, in 0.l mol/L PBS（pH =
7.0）In 0.l mol/L KCl solution, to obtained hollow CeO2Microballoon modified glassy carbon electrode carries out electrochemical ac resistance
Anti- spectrum（EIS）Characterize；Weigh respectively spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetic sample respectively about 1.0 g in
In 50 mL conical flasks, 15 mL methanol are added, the min of ultrasonic extraction 10 is mixed, takes about 10 mL solution in centrifuge tube, with
10000 r/min centrifuge 10 min, and supernatant liquor filters through 0. 45 μm of organic phase filter membranes, then takes 100 μ L accordingly to carry respectively
Take liquid to add in 3 mL measure media to be tested and analyzed.
Practical application：The electrochemical sensor of the present invention is used for the detection of actual sample, it is contained to hydroxyl in sample
The concentration of butyl benzoate is tested by differentiated pulse volt-ampere and is calculated with reference to standard samples recovery, the results are shown in Table 1.Each sample
Product parallel determination 15 times, RSD are less than 2%, illustrate the sensor favorable reproducibility.Use high performance liquid chromatography（HPLC）Determine same
The sample of sample is simultaneously compareed, and testing result is coincide very much with the sensor acquired results, be the results are shown in Table 2, is shown the sensor
It can be used in the measure of actual sample, present invention measure butyl p-hydroxybenzoate method is reliable.
Table 1 is the measurement result that the sensor detects butyl p-hydroxybenzoate in actual sample
Table 2 is the results contrast of butyl p-hydroxybenzoate content in two methods determination sample
The invention has the advantages that：（1）The present invention is with hollow CeO2Microballoon prepares letter as sensor sensing material
Just, cost is cheap, has the advantages of specific surface area is big, good conductivity and accumulation ability are strong, and using simple drop coating and evaporate molten
The method of agent can form uniform film in electrode surface, and preparation process only needs 4 min；Prepared material without it is poisonous,
Material polluting environment, being harmful to human body, it is small on the influence of operator's health, it is environmentally friendly；(2) can be notable
The electrochemical response signal of butyl p-hydroxybenzoate is improved, sensitivity for analysis is high, and the detection limit of butyl p-hydroxybenzoate can
Up to 4.15 × 10-8 mol/L；(3) analyze speed is fast, can directly determine, and the analysis time of whole sample is about 5 min, can be expired
The demand of the fast slowdown monitoring in foot scene；(4) favorable reproducibility, P-hydroxybenzoic acid in the sample of comparable sodium is determined with 20 sensors
During butyl ester, relative standard deviation（RSD）Less than 2.5%；(5) it is easy to operate, it is not necessary to special experiment condition, it is easy to carry, it is real
It is strong with property：By the sensor application in the measure of spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetics etc., pass through
Mark-on is tested, and finds recovery of standard addition between 98.2%-107%, acquired results are with using high performance liquid chromatography eligible result
It is basically identical, illustrate that sensor degree of accuracy in the measure of actual sample is good, method is reliable.
Above example only describes the preferred embodiment of the present invention, to illustrate technical scheme rather than limit
System, but several details in above-mentioned embodiment are not limited to, can be by any suitable within spirit of the invention and principle
Mode be combined, in order to avoid unnecessary repetition, no longer separately illustrate.In addition, a variety of implementations of the present invention
Combination between mode, without departing from the thought of the invention, equally it is considered as the invention disclosure of that.
Claims (4)
1. the electrochemical sensor of trace quick detection preservative butyl p-hydroxybenzoate, including working electrode, reference electrode,
To electrode；It is characterized in that：Described working electrode is that surface drop coating has electroactive very high hollow CeO2Microballoon modified membrane
Glass-carbon electrode；
The preparation method of the electrochemical sensor of described trace quick detection preservative butyl p-hydroxybenzoate, its feature exist
In comprising the following steps：
Step 1：The synthesis of Ce-Cit coordination polymer hollow microspheres
6 mmol citric acid is added in 24 mL secondary waters, 2 mmol Ce (NO3)3·6H2O adds above-mentioned under agitation
In citric acid solution, after stirring a few minutes, transfer the solution into 30 mL reactors, seal, 160 DEG C of 12 h of reaction, use
1mol/L HCl adjust pH value, and reactant quality is adjusted when necessary, and obtained product is washed several times respectively with water and ethanol, and 60
DEG C drying；
Step 2：Hollow CeO2The synthesis of microballoon
Ce-Cit coordination polymers hollow microsphere is calcined into 1.0-2.0 h at 365 DEG C and obtains object；
Step 3：Hollow CeO2The scattered pretreatment of microballoon
Weigh obtained hollow CeO in step 22Microsphere powder, secondary water is added, it is 2 mg/mL that 2 h of ultrasound, which obtain mass concentration,
Dispersion liquid, for drop coating modified electrode；
Step 4：The pretreatment of glass-carbon electrode
Removal of impurities process concretely comprises the following steps：Glass-carbon electrode is beaten with the aluminum oxide polishing powder of 0.3 μm and 0.05 μm respectively
Mill, after water rinses, then it is 1 to use volume ratio successively:1 salpeter solution, ethanol solution and secondary water is cleaned by ultrasonic 1 min；
Step 5：The preparation of electrochemical sensor
The hollow CeO that will be obtained in step 32Microballoon dispersant liquid drop is coated onto the pretreated glassy carbon electrode surface of step 4, evaporation
The electrochemical sensor of new food preservative butyl p-hydroxybenzoate is obtained after drying；
Further, the electrochemical property test of routine has been carried out to above-mentioned modified electrode, as a result well.
2. the electrochemical sensor of trace quick detection preservative butyl p-hydroxybenzoate as claimed in claim 1 is answered
With, it is characterised in that：It can be applied to detect the concentration of butyl p-hydroxybenzoate in cosmetics, food and medicine；Detected
Sample includes spiced dried beancurd, multiple fiber element complex capsule, jam and cosmetics.
3. the electrochemical sensor of trace quick detection preservative butyl p-hydroxybenzoate as claimed in claim 2 is answered
With, it is characterised in that specifically testing conditions are：
Determine medium：0.1 mol/L H2SO4；
Detect current potential：1.1 V；
Accumulating potential：0.8 V；
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s.
4. the inspection of the electrochemical sensor of trace quick detection preservative butyl p-hydroxybenzoate as claimed in claim 1
Survey method, it is characterised in that：30 μ L 0.01mol/L butyl p-hydroxybenzoate standard liquid is taken to determine medium to 3 mL
In, after stirring, gather cyclic voltammetry curve；15 μ L 0.001mol/L butyl p-hydroxybenzoate standard liquid is taken to arrive
In 3 mL measure media, after stirring, 1 min is enriched with, gathers differentiated pulse volt-ampere curve；Under 1.1 V current potentials, stirring is rich
Collect 1 min, differentiated pulse volt-ampere curve of the collection various concentrations butyl p-hydroxybenzoate on the electrochemical sensor；With
5.0 mmol/L, volume ratio 1:1 K3[Fe(CN)6]/K4[Fe(CN)6] it is probe, in 0.l mol/L, pH=7.0
In PBS and 0.l mol/L KCl solution, to obtained hollow CeO2Microballoon modified glassy carbon electrode carries out electrochemical AC impedance
EIS is composed to characterize；Weigh respectively spiced dried beancurd, multiple fiber element complex capsule, jam, cosmetic sample respectively about 1.0 g in 50 mL
In conical flask, 15 mL methanol are added, the min of ultrasonic extraction 10 is mixed, about 10 mL solution is taken in centrifuge tube, with 10000 r/
Min centrifuges 10 min, and supernatant liquor filters through 0. 45 μm of organic phase filter membranes, then takes the corresponding extract solutions of 100 μ L to add respectively
Tested and analyzed in 3 mL measure media.
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| CN109406595B (en) * | 2018-11-26 | 2020-11-03 | 阜阳师范学院 | Preparation method of electrochemical sensor for detecting butyl p-hydroxybenzoate |
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