CN111426734A - 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. The method realizes resource utilization of medium-low temperature coal tar pitch, the obtained graphene has a large specific surface area and is of a porous network structure, and the particle size of the nano Cu deposited on the surface of the electrode can be effectively controlled, so that the electron transfer efficiency of the electrode is improved. In the present invention, Cu/GE/GOn CE, the oxidation peak current and the concentration of hydroquinone are 2.0 × 10‑9～1.2×10‑6The linear relation is formed in the mol/L range, and the detection limit is 1.0 × 10‑9mol/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 rapid development of the chemical industry, the generated wastewater can cause huge pollution to the environment, particularly the wastewater containing phenol, and the phenol substances have high toxicity and are difficult to degrade, have potential threats of causing canceration, distortion and mutation, and are listed in a pollutant blacklist by a plurality of environmental health 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 seriously threatens human health when the content of the hydroquinone is too high. Therefore, the establishment of a method for quickly, conveniently and sensitively detecting the content of hydroquinone is of great significance.
The method for detecting hydroquinone comprises a chromatographic method, a spectrophotometric method, a fluorescence method, a polarography method, a chemiluminescence method and the like, and in recent years, the method for detecting hydroquinone by using a nano material modified electrode has been reported to obtain more ideal effects. Such as: in 2014, Wangxue (the construction and application research [ D ]. Shanghai: university of east China, 2014: 3-6.) found that the graphene/nano material chemically modified electrode has electrocatalytic activity on hydroquinone, can reduce the oxidation potential of the hydroquinone and improve the peak current.
The coal quality-classified grading utilization by taking medium-low temperature dry distillation 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 values, and finally the residual which exceeds 50 percent of the content of the coal tar is coal tar pitch. Coal tar pitch has been used only in the fields of paint, fuel, paving and the like for a long time, resulting in serious waste of resources and low added value. Therefore, development of deep processing of medium and low temperature coal tar pitch becomes an important way for resource utilization of waste, and preparation of graphene by taking coal tar pitch as a raw material and preparation of a nano composite material by taking graphene as a carrier are a research direction with development prospects.
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 of the modified electrode.
Aiming at the purpose, the nano Cu/graphene composite material modified electrode is prepared by the following method:
1. uniformly mixing medium-low temperature coal tar pitch with the average particle size of less 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 loading 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 the heating rate of 20-25 ℃/min, and keeping the temperature for 60-90 min; and cleaning the obtained product with hydrochloric acid and distilled water, and drying to obtain the graphene.
2. Ultrasonically dispersing the graphene prepared in the step 1 in N, N-dimethylformamide, dropwisely coating the obtained dispersion 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, preferably under the protection of nitrogen, the tubular furnace is heated to 150 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 30min, then the temperature is heated 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 m L/min.
The invention relates to application of a nano Cu/graphene composite material modified electrode in detecting hydroquinone.
The invention has the following beneficial effects:
1. the method comprises the steps of 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, preparing three-dimensional porous reticular graphene through co-carbonization, then preparing a graphene modified glassy carbon electrode (GE/GCE) through a dropping coating method, and finally electrodepositing nano Cu on the surface of the GE/GCE through a multi-potential step method to obtain the nano Cu/graphene composite material modified glassy carbon electrode (Cu/GE/GCE). The graphene prepared by the method has a large 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 that the electron transfer efficiency of the surface of the electrode is effectively improved.
2. On the Cu/GE/GCE prepared by the invention, the oxidation peak current and the concentration of the hydroquinone are 2.0 × 10-9～1.2×10-6Linear relation in mol/L range, high detection sensitivity and detection limit of 1.0 × 10-9mol/L。
3. According to the method, the medium-low temperature coal tar pitch is used as the raw material to prepare the graphene, 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 12Adsorption-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 12Adsorption-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 hydroquinone detection for Cu/GE/GCE prepared in example 1 and Cu/C/GCE prepared in comparative example 1.
FIG. 10 is a square voltammogram of Cu/GE/GCE prepared in example 1 for detecting hydroquinone at various concentrations (concentration: a.0.2; b.20; c.40; d.55; e.70; f.120(× 10)-8mol/L))。
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. Uniformly mixing 3.0g of medium-low temperature coal tar pitch (the softening point is 60-80 ℃, the content of quinoline insoluble is less than 10 percent and the content of toluene insoluble is less than 15 percent) with the average particle size of less than 10mm, 2.0g of butyl rubber, 18.0g of MgO with the average particle size of 50nm and 6.0g of KOH, putting the mixture into an iron tank, putting the iron tank into a tubular furnace, introducing nitrogen at the flow rate of 60m L/min at room temperature to remove oxygen, heating the tubular furnace to 150 ℃ at the heating rate of 5 ℃/min, keeping the temperature at 150 ℃ for 30min, heating the temperature of the tubular furnace to 800 ℃ at the heating rate of 22 ℃/min, keeping the temperature at 800 ℃ for 1h under the protection of nitrogen at the same flow rate, washing the obtained product with 2 mol/L HCl aqueous solution and distilled water to remove inorganic impurities, and drying the product in an oven at 109 ℃ for 24h to obtain the graphene.
2. Polishing Glassy Carbon Electrode (GCE) with metallographic abrasive paper, and sequentially using 0.1 μm and 0.05 μm Al2O3Polishing powder on chamois leather to a mirror surface, transferring the chamois leather to an ultrasonic water bath for cleaning, finally sequentially performing ultrasonic cleaning on mixed liquor of ethanol and secondary distilled water in a volume ratio of 1:1, mixed liquor of concentrated nitric acid and secondary distilled water in a volume ratio of 1:1 and secondary distilled water for 5min respectively, adding 0.001g of graphene prepared in the step 1 to 1m L N and N-dimethylformamide, performing ultrasonic dispersion for 30min until the solution becomes black and uniform graphene suspension, taking a pre-treated GCE electrode, transferring 5.0 mu L graphene suspension liquid drop by using a liquid transfer gun with a specification of 25 mu L, coating the graphene suspension liquid drop on the surface of the GCE electrode, naturally drying the graphene-modified glassy carbon electrode (GE/GCE), and finally performing electro-deposition 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 prepared in the same manner as in example 1 except that no butyl rubber was added. Then, a nano Cu/porous carbon composite material modified glassy carbon electrode is prepared according to the method of the step 2 in the embodiment 1 and is marked as Cu/C/GCE.
As shown in fig. 1, the graphene sheets obtained in example 1 are relatively uniformly distributed and have a three-dimensional network porous structure. Whereas the product prepared in comparative example 1 without addition of butyl rubber was predominantly porous carbon (see fig. 2). Fig. 3 shows that the graphene obtained in example 1 only contains C, Au elements, and since the graphene is subjected to gold spraying treatment before testing, a characteristic peak of Au is also present as well as a characteristic peak of C in the structure of the graphene, and the two elements are uniformly distributed, which indicates that the graphene prepared in example 1 has a uniform composition, the element dispersion reaches an atomic level, and EDS spectrum analysis and element content table (table 1) analysis thereof indicate that the graphene content is high. As can be seen from fig. 4, the graphene generates four absorption peaks. 3446cm at a-1And 2364cm at b-1The absorption peak of (2) is a stretching vibration peak of-OH bonds generated when the graphene sample absorbs water molecules in the air during placement; in addition, 1630cm at c-1Is a skeletal stretching vibration peak of an alkane C-C single bond; 660cm at d-1Is the skeleton stretching vibration peak of alkane C-C double bond. The IR spectrum shows that the sample has characteristic peaks of graphene.
Table 1 surface distribution of elements of graphene prepared in example 1
As can be seen from fig. 5 and 7, N of the graphene prepared in example 1 and the porous carbon prepared in comparative example 12The adsorption-desorption isotherms can be approximately seen as type IV adsorption isotherms, plateaus and hysteresis loops appear at higher relative pressures (0.5-0.9), and the hysteresis loop is type H3 according to IUPAC. It is illustrated that the graphene prepared in example 1 and the porous carbon prepared in comparative example 1 both have characteristics of mesoporous materials including micropores, mesopores, and macropores, but the graphite prepared in example 1The number of pore sizes of the alkenes is greatest at 4.1nm, the average pore diameter is 13.3nm (see FIG. 6), and the specific surface area is 991.6m2(g), whereas the porous carbon prepared without addition of butyl rubber in comparative example 1 had the largest number of pore sizes at 5.0nm, a mean pore size of 15.5nm (see FIG. 8), and a specific surface area of 430.9m2(ii) in terms of/g. Therefore, the graphene can be obtained by adding the butyl rubber, the aperture of the material is obviously reduced, and the specific surface area is improved.
Example 2
In the step 1 of the embodiment, 3.0g of medium-low temperature coal tar pitch (the softening point is 60-80 ℃, quinoline insoluble is less than 10%, the content of toluene insoluble is less than 15%), 1.5g of butyl rubber, 12.0g of MgO with the average particle size of 50nm and 3.0g of KOH are uniformly mixed and then put into an iron tank, the iron tank is placed into a tubular furnace, nitrogen is introduced at the room temperature at the flow rate of 60m L/min to remove oxygen, then the tubular furnace is heated to 140 ℃ at the heating rate of 3 ℃/min and is kept at 140 ℃ for 50min, the temperature of the tubular furnace is further heated to 750 ℃ at the heating rate of 20 ℃/min, and is kept at 750 ℃ for 90min, and the obtained product is always protected by nitrogen at the same flow rate, the obtained product is cleaned by using 2 mol/L HCl aqueous solution and distilled water to remove inorganic impurities, and then is dried in an oven at 109 ℃ for 24h to obtain graphene, other steps are the same as those in the example 1, and the nano Cu/graphene composite material modified glassy carbon electrode (Cu/GE/GCE.
Example 3
In the step 1 of the embodiment, 3.0g of medium-low temperature coal tar pitch (the softening point is 60-80 ℃, quinoline insoluble is less than 10%, the content of toluene insoluble is less than 15%), 3.0g of butyl rubber, 20.0g of MgO with the average particle size of 50nm and 6.0g of KOH are uniformly mixed and then put into an iron tank, the iron tank is placed into a tubular furnace, nitrogen is introduced at the room temperature at the flow rate of 60m L/min to remove oxygen, then the tubular furnace is heated to 160 ℃ at the heating rate of 8 ℃/min and is kept at 160 ℃ for 30min, the temperature of the tubular furnace is further heated to 850 ℃ at the heating rate of 25 ℃/min, and is kept at 850 ℃ for 1h under the protection of nitrogen at the same flow rate, the obtained product is cleaned by using 2 mol/L HCl aqueous solution and distilled water to remove inorganic impurities, and then is dried in an oven at 109 ℃ for 24h to obtain graphene, other steps are the same as the step of the example 1, and the 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 2.0 × 10-5Cyclic voltammetry scanning (scanning rate is 0.1V/s) is carried out in PBS buffer solution (pH 7.2) of mol/L hydroquinone, and the obtained cyclic voltammogram is shown in fig. 9.
6 hydroquinone solutions of different concentrations were prepared in PBS buffer solution (pH 7.2) and measured by square wave voltammetry using Cu/GE/GCE prepared in example 1 as the working electrode, and the results are shown in FIG. 10. The results show the oxidation peak current (I) of hydroquinonep) And its concentration (c) is 2.0 × 10-9～1.2×10-6The linear relation is in the mol/L range, and the linear regression equation is Ip＝6.592×107c+0.2015，r＝0.9985，IpThe oxidation peak current is measured in units of μ A, c is the hydroquinone concentration is measured in units of mol/L, and the detection limit is 1.0 × 10-9mol/L(S/N＝3)。
The anti-interference performance, the practical applicability and the reliability of the hydroquinone detection method are further tested:
1. interference experiment
The influence of common interfering ions in the hydroquinone determination on the determination is examined when the hydroquinone solution is 2.0 × 10-3700 times of C at mol/L2O4 2-620 times K+450 times of Mg2+、Al 3+400 times NO2 +100 times of Ca 2+30 times of Fe3+Without interference, add 7.0 × 10-5The mol/L EDTA solution can allow 26 times of Mg 2+90 times of Al3+Are present. More than 2 times catechol, 0.5 times phenol will cause interference.
2. Determination of actual samples
The hydroquinone content of a certain medical skin cream (index value: 3% (w/w)) was measured. A certain amount of sample was weighed, mixed well with PBS (pH 7.2) buffer solution by sonication for 15min, and diluted to the mark 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 measurement of Hydroquinone in medical skin cream
As can be seen from table 2, the average hydroquinone content in the samples was determined to be 3.01% (RSD ═ 1.4%), with good agreement with the indicated values.
3. Test for labeling
To investigate the reliable performance of the method, a recovery test was added to the samples and the results are shown in table 3.
TABLE 3 recovery rate test results
As can be seen from Table 3, the recovery rate of this method is 94.8% to 102.6%, indicating that the method can be used for determining the hydroquinone content in a sample.
Claims (6)
1. A preparation method of a nano Cu/graphene composite material modified electrode is characterized by comprising the following steps:
(1) uniformly mixing medium-low temperature coal tar pitch with the average particle size of less 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 loading 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 the heating rate of 20-25 ℃/min, and keeping the temperature for 60-90 min; washing the obtained product with hydrochloric acid and distilled water, and drying to obtain graphene;
(2) ultrasonically dispersing the graphene prepared in the step (1) in N, N-dimethylformamide, dropwisely coating the obtained dispersion 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 preparation method of the nano Cu/graphene composite material modified electrode according to claim 1, characterized by comprising the following steps: in the step (1), the mass ratio of the medium-low temperature coal tar pitch to the butyl rubber to the MgO to the KOH is 3:2:18: 6.
3. The preparation method of the nano Cu/graphene composite material modified electrode according to claim 1, characterized by comprising the following steps: in the step (1), heating a tube furnace to 150 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and preserving heat for 30 min; then the temperature is raised to 800 ℃ at the heating rate of 22 ℃/min, and the temperature is kept for 1 h.
4. The preparation method of the nano Cu/graphene composite material modified electrode according to claim 3, wherein in the step (1), the flow rate of nitrogen is 50-70 m L/min.
5. The nano Cu/graphene composite material modified electrode prepared by the method of any one of claims 1 to 4.
6. Use of the nano Cu/graphene composite modified electrode of claim 5 in the detection of hydroquinone.
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