CN106198666B - A kind of composite material modified glassy carbon electrode and preparation method thereof detecting lead ion - Google Patents
A kind of composite material modified glassy carbon electrode and preparation method thereof detecting lead ion Download PDFInfo
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- CN106198666B CN106198666B CN201610514521.8A CN201610514521A CN106198666B CN 106198666 B CN106198666 B CN 106198666B CN 201610514521 A CN201610514521 A CN 201610514521A CN 106198666 B CN106198666 B CN 106198666B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
Abstract
The invention discloses a kind of composite material modified glassy carbon electrodes and preparation method thereof for detecting lead ion, the composite material modified glassy carbon electrode includes glass-carbon electrode, nano ferriferrous oxide/titanium dioxide/nitrogen-doped graphene/nanogold composite material is filled in glassy carbon electrode surface, then adsorbs Organic ligand modification film.The preparation method includes step 1, amination shell core Fe3O4/TiO2Preparation；2, carboxylated nitrogen-doped graphene/nanogold preparation；3,Fe3O4/TiO2The preparation of/NG/Au composite material；4, the preparation of organic ligand (ETBD)；5,Fe3O4/TiO2The preparation of/NG/Au/ETBD modified glassy carbon electrode.Composite material modified glassy carbon electrode of the invention this have the advantage that response is rapid, at low cost, detection sensitivity is high, the range of linearity is wide, Monitoring lower-cut is low, strong antijamming capability and stability are excellent.
Description
Technical field
The invention belongs to Electroanalytical Chemistry fields, and in particular to a kind of composite material modified glassy carbon electrode and its preparation side
Method.
Background technique
With the development of modern industry, lead is widely used in chemical industry, plating, smelts the industries such as battery, therefore more next
More lead ions is entered in people's lives environmental and biological materials by all means and extended residual.Lead poisoning is to nerve
System, hematological system, digestive system etc. can cause serious harm and threaten human health.Currently, to the traditional detection of lead ion
Method has atomic absorption spectrography (AAS), inductively coupled plasma mass spectrometry, x ray fluorescence spectrometry etc., however these methods are set
It is standby expensive, complicated for operation, time-consuming, and cannot monitor on-line.Therefore, quick, accurate, sensitive, easy low concentration lead is developed
Ion detection method is important subject in recent years.
Compared with above-mentioned traditional detection method, there is electrochemical methods equipment simply, easily to automate, while have both response
The advantages such as speed is fast, at low cost, stability is good, selectivity is strong, sensitivity height, still, how to prepare a kind of can make lead ion fast
Fast, efficiently concentrating to electrode surface electrode is the problem that electrochemical technology field needs to solve.Chinese patent literature
CN104198555A disclosed on December 10th, 2014 a kind of poly- porphyrin/In Glassy Carbon Electrode Modified With Nano-gold, preparation method and its
Using, the poly- porphyrin/In Glassy Carbon Electrode Modified With Nano-gold, including glass-carbon electrode, it is deposited with nanogold particle in glassy carbon electrode surface,
It is also covered with polymerization tetraphenylporphyrin film layer.The electrode can apply in the detection of trace lead ion.The patent is able to detect lead
The lower limit value of ion is 1 × 10-8The lower limit value of mol/L, detection are still higher, need to further increase detection sensitivity.
Summary of the invention
For the technical problems in the prior art, the technical problem to be solved by the invention is to provide a kind of detections
The composite material modified glassy carbon electrode of lead ion, it is for that during detecting lead ion, can improve detection sensitivity, selection
Property, widen the range of linearity, reduce detection limit value.The present invention also provides a kind of preparation sides of composite material modified glassy carbon electrode
Method.
In order to solve the above-mentioned technical problem, the present invention also provides a kind of detection lead ion composite material modification glass carbon electricity
Pole, including glass-carbon electrode fill nano ferriferrous oxide/titanium dioxide/nitrogen-doped graphene/nanogold in glassy carbon electrode surface
Composite material, then adsorb Organic ligand modification film.
The present invention also provides a kind of preparation methods of composite material modified glassy carbon electrode for detecting lead ion, including following step
Suddenly：
Step 1：The preparation of amination shell core ferroso-ferric oxide/titanium dioxide
It is 5 that shell core nano ferriferrous oxide/titanium dioxide, which is dispersed in volume ratio,:Surpass in 1 dehydrated alcohol/water mixed liquid
Then suitable ammonium hydroxide and the stirring of (3- aminopropyl) triethoxysilane is added at least for 24 hours in sound at least 30min, product is with anhydrous
Ethyl alcohol cleaning 3 times or more, then implement drying；
Step 2：The preparation of carboxylated nitrogen-doped graphene/nanogold
By carboxylated nitrogen-doped graphene ultrasonic disperse in suitable water, pH value of solution is adjusted between 9~11 with ammonium hydroxide,
Then a certain amount of nano-Au solution is added, nitrogen reflux 10~for 24 hours, product dehydrated alcohol and water are led at 90~110 DEG C
Then washing implements drying to neutrality；
Step 3：Nano ferriferrous oxide/titanium dioxide/nitrogen-doped graphene/nanogold composite material preparation
15 parts of carboxylated nitrogen-doped graphene/nanogold are taken by mass fraction, 20 parts is added and contains 1- ethyl -3- (3- bis-
Dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and 16 parts of N- hydroxysuccinimides water in ultrasonic disperse be no less than 2h, so
After add the stirring of 15 parts of amination shell core ferroso-ferric oxides/titanium dioxide at least for 24 hours, product cleans number with dehydrated alcohol and water
It is secondary, then implement drying；
Step 4：The preparation of organic ligand ETBD
The synthesis of ETBD is in two steps：Firstly, taking bromo- 1, the 2- phenylenediamine of 10 parts of 4-, 10 parts of 1,2- second by the amount number of substance
Two mercaptan, 20 parts of K2CO3, 1 part of FeCl3·6H2O and 1 part of L-PROLINE is protected under the conditions of proper amount of methanol by N2, is heated to reflux 24
~36h.Product volume ratio is 1:1 CH2Cl2It washs and extracts with the NaOH mixed liquor of 1.5~3mol/L of concentration, organic layer is used
Anhydrous Na2SO4It is dry then to obtain product after chromatography post separation；
Secondly, taking 1 part of above-mentioned product and 2 parts of salicylides to be dissolved in dehydrated alcohol by the amount number of substance, in faintly acid
Under the conditions of be heated to reflux 6~12h, products therefrom volume ratio is 1:1 CH2Cl2/CH3It is dry after OH mixed solution recrystallization.
Step 5：Detect the preparation of the composite material modified glassy carbon electrode of lead ion
Take Fe made from step 33O4/TiO2/ NG/Au composite material be added distilled water ultrasound obtain mass concentration be 1~
Then dispersant liquid drop is filled pretreated glassy carbon electrode surface, impregnates electrode after natural drying by the dispersion liquid of 2mg/mL
In the ethanol solution of 0.05~0.1mol/L ETBD, after natural drying to obtain the final product.
Compared with prior art, the advantage of the invention is that：
1, nanogold, NG surface-active site are more, and conductive capability is strong；Fe3O4/TiO2Chemical stability is good, has to lead ion
Strong suction-operated.
2, the ETBD film layer of glassy carbon electrode surface, N and-OH in structure easily form complex compound with lead ion, improve
Detect the sensitivity of lead ion.
3, the composite material modified glassy carbon electrode of present invention detection lead ion, improves the detection water of electrochemical sensor
It is flat, maintain good current-responsive, with good stability, repeated and reliability of structure.
4, the preparation method of the composite material modified glassy carbon electrode of detection lead ion of the invention, it is simple process, at low cost
It is honest and clean, only do quickly, obtained electrode have good stability and anti-interference ability, the detected representation of trace lead ion is gone out
Excellent properties, sensitivity with higher.
5, the composite material modified glassy carbon electrode of detection lead ion of the invention is for the detection to lead ion, sensitivity
Height, the range of linearity is wide, and Monitoring lower-cut is low, with 2 × 10-8The current-responsive of the lead ion of mol/L is compared, to 1 × 10-3Mol/L's
Na+、Ca2+、Mg2+、Fe3+、Cu2+、Ag+、Mn2+、Cl-、CO3 2-、SO4 2-、NO3 -、NO2 -, 1 × 10-4The K of mol/L+, 1 × 10- 5The Co of mol/L2+、Zn2+The current-responsive of equal interfering ions can be ignored.
6, the composite material modified glassy carbon electrode of detection lead ion of the invention is still protected after storing after a period of time
Good current-responsive is held.Compared with traditional heavy metal detection method, with easy to operate, response is rapid, at low cost, detection
High sensitivity, the range of linearity are wide, Monitoring lower-cut is low, strong antijamming capability and stability are excellent.
Detailed description of the invention
Detailed description of the invention of the invention is as follows：
Fig. 1 is the synthetic route chart of ETBD；
Fig. 2 is various modified electrodes in 5mM K3[Fe(CN)6] and 0.1mol/L KCl mixed liquor in cyclic voltammogram；
In Fig. 2：a,Fe3O4/GCE, b, bare glassy carbon electrode GCE, c, Fe3O4/TiO2/ GCE, d, Fe3O4/TiO2/NG/Au/
ETBD/GCE, e, Fe3O4/TiO2/ NG/Au/GCE, f, NG/Au/GCE；
Fig. 3 is the composite material modified glassy carbon electrode of the detection lead ion of embodiment 1 using ABS as background liquid, detection range
4 × 10-13~2 × 10-8The square wave voltammogram of the lead ion solution of mol/L；
In Fig. 3：1~11 is square wave voltammetry curve corresponding to plumbum ion concentration from low to high：4×10-13, 8 ×
10-13, 8 × 10-12, 2 × 10-11, 8 × 10-11, 2 × 10-10, 8 × 10-10, 2 × 10-9, 8 × 10-9, 1.5 × 10-8With 2 × 10- 8mol/L；
Fig. 4 is the composite material modified glassy carbon electrode of the detection lead ion of embodiment 1 using ABS as background liquid, and lead ion is dense
Range is spent 4 × 10-13~2 × 10-8The Linear Fit Chart of signal is detected under mol/L；
Fig. 5 is the interfering substance current-responsive figure of the composite material modified glassy carbon electrode of the detection lead ion of embodiment 2.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples：
Embodiment 1
The composite material modified glassy carbon electrode preparation method of the detection lead ion of the present embodiment, includes the following steps：
Step 1：Amination shell core Fe3O4/TiO2Preparation
By the shell core nanometer Fe of 10mg3O4/TiO2It is dispersed in ultrasonic disperse in the mixed liquor of 25mL dehydrated alcohol and 5mL water
30min, 28% ammonium hydroxide of mass fraction and 30 μ L (3- aminopropyl) triethoxysilane that 0.3mL is then added stir for 24 hours, product
With washes of absolute alcohol 5 times, 2h is then dried at 60 DEG C.
Step 2：The preparation of carboxylated nitrogen-doped graphene/nanogold
By the carboxylated nitrogen-doped graphene ultrasonic disperse of 40mg in 40mL water, pH value of solution is adjusted to 10, so with ammonium hydroxide
The nano-Au solution of 6mL is added afterwards, leads to nitrogen reflux 10h at 100 DEG C, product dehydrated alcohol and water washing to neutrality, so
The dry 4h at 60 DEG C afterwards.
Step 3：Fe3O4/TiO2The preparation of/NG/Au composite material
1- ethyl -3- (the 3- containing 20mg is added in the carboxylated nitrogen-doped graphene/nanogold 15mg weighed in step 2
Dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and 16mg N- hydroxysuccinimides 40mL water in ultrasonic disperse 2h,
Then the amination Fe in 15mg step 1 is added3O4/TiO2For 24 hours, product dehydrated alcohol and water clean 4 times, 60 for stirring
Dry 2h at DEG C.
Step 4：The preparation of organic ligand (ETBD)
As shown in Fig. 1, the synthesis of ETBD is in two steps：Firstly, bromo- 1, the 2- phenylenediamine (1mmol) of 4-, 1,2- dithioglycol
(1mmol)、K2CO3(2mmol), FeCl3·6H2O (0.1mmol) and L-PROLINE (0.1mmol), the item of methanol (10mL)
By N under part2Protection, is heated to reflux for 24 hours at 65 DEG C.Product CH2Cl2(10mL) and NaOH (2mol/L, 10mL) washing extraction
It takes, organic layer anhydrous Na2SO4It is dry then to obtain product after chromatography post separation.
Secondly, product obtained above (0.25mmol) and salicylide (0.5mmol) are dissolved in dehydrated alcohol, weak
10h, product CH are heated to reflux under acid condition2Cl2/CH3OH=15mL：After the mixed solution recrystallization of 15mL at 50 DEG C
Drying is for 24 hours.
Step 5：Fe3O4/TiO2The preparation of/NG/Au/ETBD modified glassy carbon electrode
Weigh Fe obtained in step 33O4/TiO2/ NG/Au composite material addition distilled water ultrasound obtains mass concentration and is
Then dispersant liquid drop is filled pretreated glassy carbon electrode surface, impregnates electrode after natural drying by the dispersion liquid of 1mg/mL
In the ethanol solution of 0.1mol/L ETBD, up to Fe of the invention after natural drying3O4/TiO2/ NG/Au/ETBD is repaired
Adorn glass-carbon electrode.
Above-mentioned pretreatment glass-carbon electrode can carry out according to conventional methods in the art, in order to simplify pretreatment glass-carbon electrode
The step of, it is preferred to use following steps：Successively with 1.0 μm, 0.3 μm, 0.05 μm of Al on chamois leather2O3Powder sanding and polishing at
Mirror surface, then distilled water is cleaned by ultrasonic, and uses N2Drying；
Conventional electrochemical property test is carried out to the composite material modified glassy carbon electrode of the present embodiment, as a result well.
Embodiment 2
The preparation method of the composite material modified glassy carbon electrode of the detection lead ion of the present embodiment, according to the following steps：
Step 1：Amination shell core Fe3O4/TiO2Preparation
Unlike the first embodiment：Then product dries 6h with washes of absolute alcohol 5 times at 40 DEG C；
Step 2：The preparation of carboxylated nitrogen-doped graphene/nanogold
By the carboxylated nitrogen-doped graphene ultrasonic disperse of 100mg in 200mL water, pH value of solution is adjusted to 11 with ammonium hydroxide,
Then the nano-Au solution of 15mL is added, leads to nitrogen reflux for 24 hours at 110 DEG C, product dehydrated alcohol and water washing to neutrality,
Then the dry 6h at 50 DEG C.
Step 3：Fe3O4/TiO2The preparation of/NG/Au composite material
1- ethyl-the 3- containing 200mg is added in the carboxylated nitrogen-doped graphene/nanogold 150mg weighed in step 2
Ultrasound point in the 400mL water of the N- hydroxysuccinimides of (3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and 160mg
5h is dissipated, the amination Fe in 150mg step 1 is then added3O4/TiO236h is stirred, product cleans number with dehydrated alcohol and water
It is secondary, the dry 4h at 40 DEG C.
Step 4：The preparation of organic ligand (ETBD)
The synthesis of ETBD is in two steps：The first step unlike the first embodiment, is heated to reflux 36h at 68 DEG C.
Second step unlike the first embodiment, is heated to reflux 8h, product CH under mildly acidic conditions2Cl2/CH3OH=
150mL：36h is dried at 45 DEG C after the mixed solution recrystallization of 150mL.
Step 5 is same as Example 1.
Conventional electrochemical property test is carried out to the composite material modified glassy carbon electrode of the present embodiment, as a result well.
Electrode performance test
Electrochemical test method is carried out to electrode：
1, cyclic voltammetry is tested：
Take 30mL 5.0mM K3[Fe(CN)6] and 0.1mol/L KCl mixed liquor be background liquid, in CHI660E type electrochemistry
Surface sweeping, operating potential -0.2V-+0.8V, sweep speed 50mV/s are carried out to Different electrodes using cyclic voltammetry on work station.
Modified electrode used has (a), Fe3O4/GCE, (b), bare glassy carbon electrode GCE, (c), Fe3O4/TiO2/ GCE, (d), Fe3O4/TiO2/
NG/Au/ETBD/GCE, (e), Fe3O4/TiO2/ NG/Au/GCE, (f), NG/Au/GCE.In addition, saturation silver chlorate is reference electricity
Pole, platinum electrode are auxiliary electrode, constitute three-electrode system, and test loop volt-ampere curve is shown in Fig. 2.
As shown in Fig. 2, in background liquid, due to Fe3O4Weakly conducting rate, as electrode modification Fe3O4(after curve a), oxidation
Reduction peak reduces instead.The redox peak current ratio b's of c will be attributed to the fact that by force TiO2Outstanding conductivity.Still further aspect,
NG and Au NPs fabulous conductivity promotes electronics transfer and its redox peaks is made to increased dramatically (curve f), therefore also make
Obtain being eager to excel for the redox peak current ratio c and a of e.As the Fe of embodiment 13O4/TiO2ETBD of/the NG/Au/GCE in 0.1M is molten
It is since ETBD organic film hinders the transfer of electronics that postpeak decrease is impregnated in liquid.Find out according to the above analysis and in conjunction with Fig. 2：This
The Fe of invention3O4/TiO2/ NG/Au/ETBD modified electrode is functional.
2, square wave voltammetry detects
Using the ABS buffer solution of pH=5.00 as background liquid, certain density lead ion solution, plumbum ion concentration model are prepared
It is trapped among 4 × 10-13~2 × 10-8Mol/L takes 4 × 10 respectively-13, 8 × 10-13, 8 × 10-12, 2 × 10-11, 8 × 10-11, 2 × 10-10, 8 × 10-10, 2 × 10-9, 8 × 10-9, 1.5 × 10-8With 2 × 10-8Mol/L totally 11 kinds of concentration working solutions, with embodiment 1
Fe3O4/TiO2/ NG/Au/ETBD modified glassy carbon electrode is working electrode, and saturation silver chlorate is reference electrode, supplemented by platinum electrode
Electrode is helped, three-electrode system is constituted, is measured using square wave voltammetry, scanning voltage range is -1.6V-+0.2V, preenrichment
Time 360s, sweep speed are that 50mV/s amplitude is 25mV, and current potential pressurization is 4mV, the square wave voltammogram of above-mentioned lead ion solution
As shown in Figure 3.
As shown in figure 3, the peak current of square wave volt-ampere curve also increases as lead ion solution concentration increases, this be because
For in working solution, the Fe of lead ion and embodiment 13O4/TiO2The ETBD on/NG/Au/ETBD modified glassy carbon electrode surface points
N-H and-OH coordination in minor structure are combined and are formed complex compound, and plumbum ion concentration is higher, and binding ability is stronger, and peak current is also got over
Greatly.
As shown in figure 4, the Fe of embodiment 13O4/TiO2The line of/NG/Au/ETBD modified glassy carbon electrode detection plumbum ion concentration
Property range be 4 × 10-13~2 × 10-8Mol/L, linear equation be y (μ A)=5.0612+0.0792x (pM) and y (μ A)=
27.0354+(6.9248×10-4) x (pM), wherein y is current average when detecting to lead ion；X be solution to be measured in lead from
The concentration value of son；Related coefficient is respectively 0.9979 and 0.9983；Monitoring lower-cut is 7.5 × 10-13(S/N=3 refers to meter to mol/L
Calculating detection limit is calculated under conditions of signal-to-noise ratio is 3).It follows that the Fe in embodiment 13O4/TiO2/NG/Au/ETBD
The detection range of linearity of modified electrode is wide, high sensitivity, detection limit are low, good to lead ion detection performance.
So the Fe of embodiment 13O4/TiO2/ NG/Au/ETBD modified glassy carbon electrode is able to achieve to low concentration lead ion
Trace detection.
3, the lead ion selectivity test under interfering substance
Using the Fe of embodiment 23O4/TiO2/ NG/Au/ETBD modified glassy carbon electrode, test method are as follows：
Using the ABS buffer solution of pH=5.00 as background liquid, 2 × 10 are prepared-8Mol/L lead ion solution, 1 × 10-3mol/
The Na of L+、Ca2+、Mg2+、Fe3+、Cu2+、Ag+、Mn2+、Cl-、CO3 2-、SO4 2-、NO3 -、NO2 -Solution, 1 × 10-4The K of mol/L+It is molten
Liquid, 1 × 10-5The Co of mol/L2+、Zn2+Solution and its all mixed liquors totally 17 kinds of working solutions, with the Fe of embodiment 23O4/TiO2/
NG/Au/ETBD modified glassy carbon electrode is working electrode, and saturation silver chlorate is reference electrode, and platinum electrode is auxiliary electrode, is constituted
Three-electrode system is measured using square wave voltammetry, and scanning voltage range is -1.6V-+0.2V, and preenrichment time 360s is swept
It is 25mV that retouch rate, which be 50mV/s amplitude, and current potential pressurization is 4mV, and current-responsive figure is as shown in Figure 5.
As shown in figure 5, interference cation is respectively (1-1) K+, (1-2) Na+, (1-3) Ca2+, (1-4) Mg2+, (1-5) Zn2 +, (1-6) Fe3+, (1-7) Cu2+, (1-8) Ag+, (1-9) Co2+, (1-10) Mn2+(1-11) Pb2+；
Interfering anion is respectively (2-6) Cl-, (2-7) CO3 2-, (2-8) SO4 2-, (2-9) NO3 -, (2-10) NO2 -(2-
11)Pb2+；
Mixed solution is (3-10) Pb2+, (3-11) all zwitterions and Pb2+Mixed solution；
As can be seen from Figure 5：Fe of the invention3O4/TiO2/ NG/Au/ETBD modified glassy carbon electrode rings the electric current of interfering ion
It answers minimum, compared with lead ion current-responsive, can almost ignore；The electric current of individual lead ion current-responsive and mixed solution
Response within ± 5.24%, shows Fe of the invention compared to variation3O4/TiO2/ NG/Au/ETBD modified glassy carbon electrode has good
Good anti-interference has high selectivity to lead ion detection.
Claims (3)
1. a kind of composite material modified glassy carbon electrode for detecting lead ion, including glass-carbon electrode, it is characterized in that：In glass-carbon electrode table
Face fills nano ferriferrous oxide/titanium dioxide/nitrogen-doped graphene/nanogold composite material, then adsorbs Organic ligand modification
Film；Nano ferriferrous oxide/titanium dioxide/nitrogen-doped graphene/the nanogold composite material is made by following steps：
Step 1, the preparation of amination shell core ferroso-ferric oxide/titanium dioxide
It is 5 that shell core nano ferriferrous oxide/titanium dioxide, which is dispersed in volume ratio,:In 1 dehydrated alcohol/water mixed liquid ultrasound extremely
Then suitable ammonium hydroxide and the stirring of (3- aminopropyl) triethoxysilane is added at least for 24 hours, product dehydrated alcohol in few 30min
Cleaning 3 times or more, then implement drying；
Step 2, the preparation of carboxylated nitrogen-doped graphene/nanogold
By carboxylated nitrogen-doped graphene ultrasonic disperse in suitable water, pH value of solution is adjusted between 9~11 with ammonium hydroxide, then
A certain amount of nano-Au solution is added, nitrogen reflux 10~for 24 hours, product dehydrated alcohol and water washing are led at 90~110 DEG C
To neutrality, then implement drying；
Step 3, nano ferriferrous oxide/titanium dioxide/nitrogen-doped graphene/nanogold composite material preparation
15 parts of carboxylated nitrogen-doped graphene/nanogold are taken by mass fraction, 20 parts is added and contains 1- ethyl -3- (3- dimethyl
Aminopropyl) phosphinylidyne diimmonium salt hydrochlorate and 16 parts of N- hydroxysuccinimides water in ultrasonic disperse be no less than 2h, then again
15 parts of amination shell core ferroso-ferric oxides/titanium dioxide stirring is added at least for 24 hours, product dehydrated alcohol and water clean for several times,
Then implement drying.
2. a kind of preparation method of composite material modified glassy carbon electrode described in claim 1, characterized in that including following step
Suddenly：
The synthesis of step 1, organic ligand ETBD
Firstly, taking bromo- 1, the 2- phenylenediamine of 10 parts of 4-, 10 parts of 1,2- dithioglycols, 20 parts of K by the amount number of substance2CO3, 1 part
FeCl3·6H2O and 1 part of L-PROLINE, by N under the conditions of proper amount of methanol2Protection, is heated to reflux 24~36h；Product is with volume ratio
1:1 CH2Cl2It washs and extracts with the NaOH mixed liquor of 1.5~3mol/L of concentration, organic layer anhydrous Na2SO4It is dry then to pass through
Product is obtained after chromatography post separation；
Secondly, taking 1 part of above-mentioned product and 2 parts of salicylides to be dissolved in dehydrated alcohol by the amount number of substance, in solutions of weak acidity
Under be heated to reflux 6~12h, products therefrom volume ratio is 1:1 CH2Cl2/CH3It is dry after OH mixed solution recrystallization；
Step 2, detect lead ion composite material modified glassy carbon electrode preparation
It takes nano ferriferrous oxide/titanium dioxide/nitrogen-doped graphene/nanogold composite material that distilled water ultrasound is added and obtains matter
The dispersion liquid that concentration is 1~2mg/mL is measured, dispersant liquid drop is then filled into pretreated glassy carbon electrode surface, after natural drying
Electrode is immersed in the ethanol solution of 0.05~0.1mol/L ETBD, after natural drying to obtain the final product.
3. the preparation method of composite material modified glassy carbon electrode according to claim 2, it is characterized in that：Pre-process glass carbon electricity
Pole is on chamois leather successively with 1.0 μm, 0.3 μm, 0.05 μm of Al2O3Powder sanding and polishing is at mirror surface, and then distilled water ultrasound is clear
It washes, and uses N2Drying.
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| CN101105472A (en) * | 2007-06-11 | 2008-01-16 | 大连理工大学 | Water body chemical oxygen demand electrochemical measuring method |
| CN101706471A (en) * | 2008-12-12 | 2010-05-12 | 烟台海岸带可持续发展研究所 | Electrochemical sensor for determining concentration of heavy metal ions in water sample |
| CN104409703A (en) * | 2014-11-24 | 2015-03-11 | 天津大学 | Preparation method for molybdenum disulfide/nitrogen-doped graphene three-dimensional composite material and application of molybdenum disulfide/nitrogen-doped graphene three-dimensional composite material |
| CN104474980A (en) * | 2014-11-07 | 2015-04-01 | 中南大学 | Supermolecule hybridized hydrogel, graphene aerogel, preparation methods and application of two |
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Patent Citations (4)
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| CN101105472A (en) * | 2007-06-11 | 2008-01-16 | 大连理工大学 | Water body chemical oxygen demand electrochemical measuring method |
| CN101706471A (en) * | 2008-12-12 | 2010-05-12 | 烟台海岸带可持续发展研究所 | Electrochemical sensor for determining concentration of heavy metal ions in water sample |
| CN104474980A (en) * | 2014-11-07 | 2015-04-01 | 中南大学 | Supermolecule hybridized hydrogel, graphene aerogel, preparation methods and application of two |
| CN104409703A (en) * | 2014-11-24 | 2015-03-11 | 天津大学 | Preparation method for molybdenum disulfide/nitrogen-doped graphene three-dimensional composite material and application of molybdenum disulfide/nitrogen-doped graphene three-dimensional composite material |
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| A sensitive electrochemical sensor for lead based on gold nanoparticles/nitrogen-doped graphene composites functionalized with L-cysteine-modified electrode;Yan-mei Cheng等;《J Solid State Electrochem》;20151006;第20卷;摘要，第328-329页 * |
| Preparation of magnetic Fe3O4/TiO2/Ag composite microspheres with enhanced photocatalytic activity;Li Zhang等;《Solid State Sciences》;20151217;第52卷;第42-48页 * |
| Selective detection toward Cd2+ using Fe3O4/RGO nanoparticle modified glassy carbon electrode;Yu-Feng Sun等;《Journal of Electroanalytical Chemistry》;20140103;第714-715卷;第97–102页 * |
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