CN111426734B - Nano Cu/graphene composite material modified electrode, preparation method thereof and application of nano Cu/graphene composite material modified electrode in detection of hydroquinone - Google Patents
Nano Cu/graphene composite material modified electrode, preparation method thereof and application of nano Cu/graphene composite material modified electrode in detection of hydroquinone Download PDFInfo
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Abstract
The invention discloses a nano Cu/graphene composite material modified electrode, a preparation method thereof and application of detecting hydroquinone, wherein three-dimensional porous reticular graphene is prepared by co-carbonization by taking medium-low temperature coal tar pitch as a raw material, butyl rubber as a modifier, KOH as an activator and nano MgO as a template, then a graphene modified glassy carbon electrode (GE/GCE) is prepared by adopting a surface dripping method, and finally nano Cu is deposited on the surface of the GE/GCE by adopting a multi-potential step method, so that the nano Cu/graphene composite material modified glassy carbon electrode (Cu/GE/GCE) is obtained. The invention realizes the resource utilization of medium-low temperature coal tar pitch, the obtained graphene has larger specific surface area and a porous net structure, and the particle size of nano Cu deposited on the surface of the electrode can be effectively controlled so as to improve the electron transfer efficiency of the electrode. On the Cu/GE/GCE of the present invention, the peak current and concentration of hydroquinone were 2.0X10 ‑9 ～1.2×10 ‑6 The detection limit is 1.0X10 in linear relation in mol/L ‑9 mol/L。
Description
Technical Field
The invention relates to a nano Cu/graphene composite material modified electrode, a preparation method of the modified electrode and application of the modified electrode in hydroquinone detection.
Background
With the great development of the chemical industry, the generated wastewater can cause great pollution to the environment, especially the wastewater containing phenol, which has great toxicity and difficult degradation, has potential threat of causing canceration, distortion and mutation, and is listed in a pollutant blacklist by a plurality of environmental sanitation organizations. Hydroquinone is widely applied to the fields of chemical production, food additives, cosmetics, medicines and the like, plays an important role in human life, but when the content of hydroquinone is too high, the hydroquinone seriously threatens the health of human bodies. Therefore, the establishment of a rapid, simple and sensitive method for detecting the hydroquinone content has important significance.
Methods for detecting hydroquinone include chromatography, spectrophotometry, fluorescence, polarography, chemiluminescence, etc., and in recent years, it has been reported that a nanomaterial-modified electrode is used to detect hydroquinone, and a relatively ideal effect is obtained. Such as: wang Xue (construction and application research [ D ] Shanghai: university of eastern China, 2014:3-6.) of the graphene/nanomaterial chemically modified electrode finds that the graphene/nanomaterial chemically modified electrode has electrocatalytic activity on hydroquinone, can reduce oxidation potential and improve peak current.
The coal quality-dividing and grading utilization by taking medium-low temperature carbonization as a core technology can generate a large amount of coal tar, the coal tar can be separated and purified to obtain a plurality of fine chemicals with high added value, and finally, the residue with the content exceeding 50% of the coal tar is the coal tar pitch. For a long time, the coal tar pitch is only used in the fields of paint, fuel, pavement and the like, so that serious resource waste and low added value are caused. Therefore, developing deep processing of medium and low temperature coal tar pitch has become an important way for recycling waste, wherein preparing graphene by taking coal tar pitch as a raw material and preparing a nanocomposite by taking graphene as a carrier is a research direction with a very development prospect.
Disclosure of Invention
The invention aims to provide a nano Cu/graphene composite material modified electrode, a preparation method of the modified electrode and a new application for the modified electrode.
Aiming at the purposes, the nano Cu/graphene composite material modified electrode is prepared by the following method:
1. uniformly mixing medium and low temperature coal tar pitch with the average particle size smaller than 10mm, butyl rubber, mgO with the average particle size of 40-60 nm and KOH according to the mass ratio of 3:1.5-3:12-20:3-6, then filling the mixture into an iron tank, placing the iron tank into a tubular furnace, heating the tubular furnace to 140-160 ℃ at the heating rate of 3-8 ℃/min under the protection of nitrogen, and preserving heat for 30-50 min; heating to 750-850 ℃ at a heating rate of 20-25 ℃/min, and preserving heat for 60-90 min; and washing the obtained product with hydrochloric acid and distilled water, and drying to obtain the graphene.
2. And (3) ultrasonically dispersing the graphene prepared in the step (1) in N, N-dimethylformamide, coating the dispersed liquid on the surface of a glassy carbon electrode to prepare a graphene modified electrode, and electrodepositing nano Cu on the surface of the graphene modified glassy carbon electrode by adopting a multi-potential step method to prepare the nano Cu/graphene composite material modified electrode.
In the step 1, the mass ratio of the medium-low temperature coal tar pitch, the butyl rubber, the MgO and the KOH is preferably 3:2:18:6.
In the step 1, it is further preferable that the tube furnace is heated to 150 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and the tube furnace is kept for 30min; then the temperature is raised to 800 ℃ at the heating rate of 22 ℃/min, and the temperature is kept for 1h. Wherein the flow rate of nitrogen is preferably 50-70 mL/min.
The invention relates to application of a nano Cu/graphene composite material modified electrode in detecting hydroquinone.
The beneficial effects of the invention are as follows:
1. according to the preparation method, medium-low temperature coal tar pitch is used as a raw material, butyl rubber is used as a modifier, KOH is used as an activator, nano MgO is used as a template, three-dimensional porous reticular graphene is prepared through co-carbonization, then a graphene modified glassy carbon electrode (GE/GCE) is prepared through a dripping method, and finally nano Cu is electrodeposited on the surface of the GE/GCE through a multi-potential step method, so that the nano Cu/graphene composite material modified glassy carbon electrode (Cu/GE/GCE) is obtained. The graphene prepared by the method has larger specific surface area, comprises macropores, mesopores and micropores, and can effectively control the particle size of Cu deposited on the surface of the electrode by taking the graphene as a carrier so as to effectively improve the electron transfer efficiency of the surface of the electrode.
2. On the Cu/GE/GCE prepared by the method, the oxidation peak current and the concentration of hydroquinone are 2.0X10 -9 ～1.2×10 -6 The detection sensitivity is high, and the detection limit is 1.0X10 when the mol/L range is in linear relation -9 mol/L。
3. According to the invention, the graphene is prepared from the medium-low temperature coal tar pitch as a raw material, so that the resource utilization of the medium-low temperature coal tar pitch is realized.
Drawings
Fig. 1 is an SEM image of graphene prepared in example 1.
Fig. 2 is an SEM image of graphene prepared in comparative example 1.
Fig. 3 is an EDS diagram of graphene prepared in example 1.
Fig. 4 is an infrared spectrum of graphene prepared in example 1.
FIG. 5 is N of graphene prepared in example 1 2 Adsorption-desorption isotherm plot.
Fig. 6 is a pore size distribution diagram of graphene prepared in example 1.
FIG. 7 is N of porous carbon prepared in comparative example 1 2 Adsorption-desorption isotherm plot.
Fig. 8 is a pore size distribution diagram of the porous carbon prepared in comparative example 1.
FIG. 9 is a cyclic voltammogram of the Cu/GE/GCE prepared in example 1 and the Cu/C/GCE prepared in comparative example 1 for detecting hydroquinone.
FIG. 10 is a square wave voltammogram of the Cu/GE/GCE of example 1 for detecting hydroquinone at various concentrations (concentration: a.0.2; b.20; c.40; d.55; e.70; f.120 (. Times.10) -8 mol/L))。
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
1. 3.0g of medium and low temperature coal tar pitch with the average particle size smaller than 10mm (softening point 60-80 ℃, quinoline insoluble matter less than 10 percent, toluene insoluble matter content less than 15 percent), 2.0g of butyl rubber, 18.0g of MgO with the average particle size of 50nm and 6.0g of KOH are uniformly mixed and then are filled into an iron tank, the iron tank is placed into a tube furnace, nitrogen is introduced at the room temperature at the flow rate of 60mL/min for deoxidization, and then the tube furnace is heated to 150 ℃ at the heating rate of 5 ℃/min and kept at the temperature of 150 ℃ for 30min; the tube furnace temperature was then raised to 800 c at a heating rate of 22 c/min and maintained at 800 c for 1 hour. During which the same flow rate of nitrogen was used. The obtained product is washed by 2mol/L HCl aqueous solution and distilled water to remove inorganic impurities, and then dried in an oven at 109 ℃ for 24 hours to obtain graphene.
2. The Glassy Carbon Electrode (GCE) was polished with metallographic sandpaper followed by sequential polishing with 0.1 μm and 0.05 μm Al 2 O 3 Polishing the powder on chamois leather to a mirror surface, transferring into an ultrasonic water bath for cleaning, and finally sequentially carrying out ultrasonic cleaning on the powder for 5min by using a mixed solution of ethanol and secondary distilled water in a volume ratio of 1:1, a mixed solution of concentrated nitric acid and secondary distilled water in a volume ratio of 1:1, and secondary distilled water. 0.001g of graphene prepared in step 1 was added to 1mL of N, N-dimethylformamide and dispersed ultrasonically for 30min until the solution became a black uniform graphene suspension. And taking the pretreated GCE electrode, using a 25 mu L-specification pipetting gun to transfer 5.0 mu L of graphene suspension liquid to be dripped on the surface of the GCE electrode, naturally air-drying to obtain a graphene modified glassy carbon electrode (GE/GCE), and finally electrodepositing nano Cu on the surface of the GE/GCE by adopting a multi-potential step method to obtain the nano Cu/graphene composite material modified glassy carbon electrode (Cu/GE/GCE).
Comparative example 1
In step 1 of example 1, porous carbon was produced in the same manner as in example 1, except that butyl rubber was not added. Then, a nano Cu/porous carbon composite modified glassy carbon electrode, designated Cu/C/GCE, was prepared according to the method of step 2 of example 1.
As shown in fig. 1, the graphene sheets obtained in example 1 are distributed uniformly and have a three-dimensional network porous structure. Whereas the product prepared without the addition of butyl rubber in comparative example 1 was mainly porous carbon (see FIG. 2). Fig. 3 shows that the graphene obtained in example 1 contains only C, au elements, and the graphene is subjected to metal spraying treatment before testing, so that not only the characteristic peak of C but also the characteristic peak of Au appear in the structure of the graphene, and the two elements are uniformly distributed, which indicates that the graphene prepared in example 1 is uniform in composition, and the element dispersion reaches an atomic level, and EDS spectrum analysis and element content table (table 1) analysis thereof show that the graphene content is higher. As can be seen from fig. 4, graphene produces four absorption peaks. 3446cm at a -1 And 2364cm at b -1 The absorption peak of (2) is a stretching vibration peak of-OH bond generated by absorbing water molecules in the air in the placing process of the graphene sample; in addition, 1630cm at c -1 Is a skeleton stretching vibration peak of alkane C-C single bond; 660cm at d -1 Is the framework stretching vibration peak of alkane C-C double bond. The IR spectrum illustrates that the sample has a characteristic peak of graphene.
Table 1 surface distribution of elements of graphene prepared in example 1
As can be seen from fig. 5 and 7, the graphene prepared in example 1 and the N of the porous carbon prepared in comparative example 1 2 The adsorption-desorption isotherms can be approximately seen as IV-type adsorption isotherms, and a platform and a hysteresis loop are both present at a relatively high pressure (0.5-0.9), and the hysteresis loop is H3-type according to IUPAC. Illustration the graphene prepared in example 1 and the porous carbon prepared in comparative example 1 both have the characteristics of mesoporous materials including micropores, mesopores and macropores, but the graphene prepared in example 1 has a pore size of maximum number at 4.1nm, an average pore size of 13.3nm (see fig. 6), and a specific surface area of 991.6m 2 Per g, whereas the porous carbon prepared in comparative example 1 without the addition of butyl rubber had a pore size of the largest amount at 5.0nm, an average pore size of 15.5nm (see FIG. 8), and a specific surface area of 430.9m 2 And/g. Therefore, the graphene can be obtained by adding the butyl rubber, the pore diameter of the material is obviously reduced, and the specific surface area is improved.
Example 2
In step 1 of this example, 3.0g of medium and low temperature coal tar pitch (softening point 60 to 80 ℃ C.; quinoline insoluble content < 10%; toluene insoluble content < 15%), 1.5g of butyl rubber, 12.0g of MgO with average particle size of 50nm, and 3.0g of KOH were mixed uniformly and then charged into an iron tank, and the iron tank was placed in a tube furnace, deoxygenated by introducing nitrogen at a flow rate of 60mL/min at room temperature, and then the tube furnace was heated to 140℃at a heating rate of 3℃per min and maintained at 140℃for 50min; the tube furnace temperature was then raised to 750 ℃ at a 20 ℃/min ramp rate and maintained at 750 ℃ for 90 minutes. During which the same flow rate of nitrogen was used. The obtained product is washed by 2mol/L HCl aqueous solution and distilled water to remove inorganic impurities, and then dried in an oven at 109 ℃ for 24 hours to obtain graphene. Other steps are the same as in example 1, and a nano Cu/graphene composite material modified glassy carbon electrode (Cu/GE/GCE) is obtained.
Example 3
In step 1 of this example, 3.0g of medium and low temperature coal tar pitch (softening point 60 to 80 ℃ C.; quinoline insoluble content < 10%; toluene insoluble content < 15%), 3.0g of butyl rubber, 20.0g of MgO with average particle size of 50nm, and 6.0g of KOH were mixed uniformly and then charged into an iron tank, and the iron tank was placed in a tube furnace, deoxygenated by introducing nitrogen at a flow rate of 60mL/min at room temperature, and then the tube furnace was heated to 160℃at a heating rate of 8℃per min and maintained at 160℃for 30min; the tube furnace temperature was then raised to 850 ℃ at a rate of 25 ℃/min and maintained at 850 ℃ for 1 hour. During which the same flow rate of nitrogen was used. The obtained product is washed by 2mol/L HCl aqueous solution and distilled water to remove inorganic impurities, and then dried in an oven at 109 ℃ for 24 hours to obtain graphene. Other steps are the same as in example 1, and a nano Cu/graphene composite material modified glassy carbon electrode (Cu/GE/GCE) is obtained.
Example 4
The modified electrodes prepared in example 1 and comparative example 1 were inserted in a 2.0X10-way -5 Cyclic voltammograms (scan rate 0.1V/s) were performed in a PBS buffer of mol/L hydroquinone (ph=7.2) and the cyclic voltammograms obtained are shown in fig. 9. The result shows that on the Cu/GE/GCE prepared in the example 1, the hydroquinone peak current is obviously increased, which proves that the nano Cu/graphene composite material modified electrode has good electrocatalytic effect.
6 hydroquinone solutions of different concentrations were prepared with PBS buffer at ph=7.2, and the Cu/GE/GCE prepared in example 1 was measured as a working electrode by square wave voltammetry, and the results are shown in fig. 10. The results show that the peak current of oxidation of hydroquinone (I p ) And its concentration (c) is 2.0X10 -9 ～1.2×10 -6 The mol/L range is in a linear relation, and a linear regression equation is as follows: i p ＝6.592×10 7 c+0.2015，r＝0.9985，I p The oxidation peak current is expressed in mu A, the hydroquinone concentration is expressed in mol/L, and the detection limit is 1.0X10 -9 mol/L(S/N＝3)。
Further, the anti-interference performance, the practical applicability and the reliability of the hydroquinone detection method are tested:
1. interference experiment
The influence of common interfering ions in hydroquinone determination on the determination is examined. When the hydroquinone solution is 2.0X10 -3 At mol/L, 700 times C 2 O 4 2- K620 times + 450 times of Mg 2+ 、Al 3+ 400 times NO 2 + 100 times of Ca 2+ 30 times of Fe 3+ Without interference. Adding 7.0X10 -5 mol/LEDTA solution, 26 times of Mg can be allowed 2+ 90 times of Al 3+ Exists. Catechol greater than 2 times, phenol 0.5 times may interfere.
2. Actual sample measurement
The hydroquinone content in a certain medical skin ointment (marked value: 3% (w/w)) was detected. A certain amount of sample was weighed, mixed well with PBS (ph=7.2) buffer solution for 15min by sonication, diluted to scale with PBS in a volumetric flask. The hydroquinone content of the sample was measured by the method of example 2, and the results are shown in Table 2.
Table 2 determination of hydroquinone in medical skin cream
As can be seen from table 2, the average hydroquinone content in the sample was 3.01% (rsd=1.4%) and the sample was well-conformed to the labeling value.
3. Label adding test
To examine the reliability of the method, recovery tests were carried out on the samples, and the results are shown in Table 3.
TABLE 3 recovery rate experimental results
As can be seen from Table 3, the recovery rate of the method is 94.8% -102.6%, which shows that the method can be used for measuring the hydroquinone content in the sample.
Claims (5)
1. The preparation method of the nano Cu/graphene composite material modified electrode is characterized by comprising the following steps of:
(1) Uniformly mixing medium and low temperature coal tar pitch with the average particle size smaller than 10mm, butyl rubber, mgO with the average particle size of 40-60 nm and KOH according to the mass ratio of 3:2:18:6, then filling the mixture into an iron tank, placing the iron tank into a tube furnace, heating the tube furnace to 140-160 ℃ at the heating rate of 3-8 ℃/min under the protection of nitrogen, and preserving heat for 30-50 min; heating to 750-850 ℃ at a heating rate of 20-25 ℃/min, and preserving heat for 60-90 min; washing the obtained product with hydrochloric acid and distilled water, and drying to obtain graphene;
(2) And (3) ultrasonically dispersing the graphene prepared in the step (1) in N, N-dimethylformamide, coating the dispersed liquid on the surface of a glassy carbon electrode to prepare a graphene modified electrode, and electrodepositing nano Cu on the surface of the graphene modified glassy carbon electrode by adopting a multi-potential step method to prepare the nano Cu/graphene composite material modified electrode.
2. The method for preparing the nano Cu/graphene composite modified electrode according to claim 1, wherein the method comprises the following steps: in the step (1), under the protection of nitrogen, heating the tube furnace to 150 ℃ at a heating rate of 5 ℃/min, and preserving heat for 30min; then the temperature is raised to 800 ℃ at the heating rate of 22 ℃/min, and the heat is preserved for 1h.
3. The method for preparing the nano Cu/graphene composite modified electrode according to claim 2, wherein the method comprises the following steps: in the step (1), the flow rate of nitrogen is 50-70 mL/min.
4. The nano Cu/graphene composite material modified electrode prepared by the method of any one of claims 1 to 3.
5. The use of the nano Cu/graphene composite modified electrode of claim 4 in detecting hydroquinone.
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