CN108318551A - A kind of hercynite composite material, hercynite composite material modified glassy carbon electrode and its preparation method and application - Google Patents
A kind of hercynite composite material, hercynite composite material modified glassy carbon electrode and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of hercynite composite materials, hercynite composite material modified glassy carbon electrode and its preparation method and application.The preparation method of the hercynite composite material includes：Iron nitrate solution and aluminum nitrate solution are mixed, then stirred at 60~80 DEG C, xerogel is obtained, then will be calcined after xerogel grind into powder, hercynite is made；Aluminum nitrate and urea are mixed with graphene oxide water solution, then kept the temperature at 150~200 DEG C, using centrifugal treating, hydrated alumina redox graphene composite material is made；Hercynite is mixed with hydrated alumina redox graphene composite material with ethyl alcohol, it is then dry at 60~100 DEG C, hercynite composite material is made.Present invention hercynite composite material modified glassy carbon electrode, and it is applied to detection heavy metal ion, have many advantages, such as that detection limit is low, detection range is wide, anti-interference is good and reproducibility is good.
Description
Technical field
The invention belongs to electrochemical sensing technical field more particularly to a kind of hercynite composite material, iron aluminium point are brilliant
Stone composite material modified glassy carbon electrode and preparation method thereof and hercynite composite material modified glassy carbon electrode are quickly detecting
Application in solution in heavy metal ion.
Background technology
In recent years, environmental problem is increasingly valued by people, in soil that industrial pollution causes, water resource extensively
The problem of distribution excess heavy metal ion, is urgently to be resolved hurrily.The intake of some heavy metal ion can seriously endanger the mankind and other dynamic plants
The viable organism of object.For human body, toxic heavy metal element mainly by alimentary canal, respiratory tract, some can also to pass through skin
The approach such as skin enter human body, and mainly remain in the organ-tissues such as liver, kidney, brain, are then made to these human organs when excessive
Lead to functional lesion at murder by poisoning, when serious until completely losing.For plant, heavy metal ion is mainly inhaled by plant root
It takes in plant, growth and development that is excessive then directly affecting plant, the withered, dead of plant is caused when serious.Heavy metal
Ion is not easy to be degraded, and is difficult to clean off once accumulation.Therefore, seek a kind of fast and convenient these environmental contaminants of detection
Analysis method is extremely important.
Prodigious progress has been achieved currently for detection heavy metal ion, many detection techniques are applied,
Main method includes：Atomic fluorophotometry, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma hair
Penetrate spectroscopic methodology, high performance liquid chromatography, enzyme assay and biosensor etc..These methods are applying upper comparative maturity, but its
Instrument price costliness, processing procedure very complicated are not suitable for carrying out in-situ study.In view of the above deficiency, the following heavy metal analysis
The developing direction of technology should to the simple portable, high sensitivity of required equipment and stability is strong, testing result favorable reproducibility, institute
It needs direction at low cost to develop, and the research of continuous on-line monitoring technique should be dedicated to emphatically.Electrochemical method has because of it
There is low detection limit, low cost, simply and easily operate and analyze and sent out in the detection field of heavy metal ion in real time
Wave important function.In all electrochemical methods, stripping volt ampere analysis is widely regarded as measuring having for heavy metal ion
Power tool.
Electrochemical method has been widely studied, and how design work electrode is in modified electrode detection heavy metal ion
One most important problem selects suitable working electrode to become the most important thing.It selects to should be taken into account leading for material when material
Electrically, the factors such as cost, toxicity, chemical stability.
Be presently used for heavy metal ion in detection solution electrode material have carbon (C), golden (Au), platinum (Pt), mercury (Hg),
Redox graphene (rGO) and some metal oxides include ferroso-ferric oxide (Fe3O4) and the conducts such as magnesia (MgO)
The electrode of trim.The conductive superior, large specific surface area of redox graphene (rGO), the feature of stabilization, as function
Nano material is much applied, and in terms of electrochemical sensor, graphene film and graphite alkenyl nanometer materials also obtain
Extensive research.It is well known, however, that redox graphene tends to aggregation and redox graphene on piece does not almost have
There is functional group, limits the application of redox graphene to a certain extent.Hydrated alumina (γ-AlOOH) be it is a kind of very
Good sorbing material, containing the hydroxyl (- OH) for being largely used to adsorbing metal ions, hydrated alumina also has thermal stability good,
It is at low cost, the controllable advantage of synthetic method.Currently, hydrated alumina-redox graphene composite material (AlOOH-rGO) or
Ferroso-ferric oxide-redox graphene composite material (Fe3O4- rGO) as electrode modification object raising Electrochemical Detection performance
Research is also concerned.But above-mentioned trim modified electrode is used to there is manufacture work in the application as electrochemical sensor
Skill is complicated, of high cost, pollution environment, anti-interference difference and it is unstable etc. the shortcomings that.
Hercynite (FeAl2O4), a kind of novel semiconductor material has high reducing power, however hercynite
Energy gap be 1.7eV, the quick of photoelectron and hole compound largely hinders its chemical property.Iron aluminium at present
Spinel is mostly applied in high-temperature refractory.
Invention content
To solve the problems, such as one or more, the object of the present invention is to provide a kind of novel hercynite composite materials
(FeAl2O4- AlOOH-rGO) and preparation method thereof and utilize the novel hercynite composite material modified glassy carbon electrode,
A kind of novel electrode material is obtained for quickly detecting the heavy metal ion in solution.Hercynite prepared by the present invention is multiple
Condensation material modified glassy carbon electrode in quickly detection solution there is high sensitivity, at low cost, detection to limit low, inspection in heavy metal ion
Survey the advantages that range is wide, anti-interference is good and reproducibility is good.
The present invention provides a kind of preparation method of hercynite composite material in first aspect, and the method includes such as
Lower step：
(1) iron nitrate solution and aluminum nitrate solution are mixed, obtains the first mixed liquor, then first mixed liquor exists
Stirred under the conditions of 60~80 DEG C, obtain iron-aluminium oxide xerogel, then by the iron-aluminium oxide xerogel grind into powder it
After calcined, be made hercynite；
(2) aluminum nitrate and urea are uniformly mixed with graphene oxide water solution, obtain the second mixed liquor, it then will be described
Second mixed liquor keeps the temperature 9~12h under the conditions of 150~200 DEG C and then removes liquid by centrifugal treating, and hydration oxygen is made
Change aluminium-redox graphene composite material；With
(3) with ethyl alcohol by hydrated alumina-reduction-oxidation made from hercynite made from step (1) and step (2)
Graphene composite material is uniformly mixed, and obtains third mixed liquor, then does the third mixed liquor under the conditions of 60~100 DEG C
Hercynite composite material is made in dry 10~16h.
Preferably, the method is before carrying out step (3), further include by hercynite made from step (1) successively
Carry out wet ball grinding and dry step：The time of the wet ball grinding is 18~30h.
Preferably, the method further includes by hydrated alumina-reduction made from step (2) before carrying out step (3)
The step that graphene oxide composite material is washed and dried successively.
Preferably, the temperature calcined in step (1) is 600~900 DEG C, and the time of calcining is 1~3h；Institute in step (1)
State that iron nitrate solution is iron nitrate aqueous solution and/or aluminum nitrate solution is aluminum nitrate aqueous solution；Ferric nitrate described in step (1)
The mass ratio of the ferric nitrate contained in solution and the aluminum nitrate contained in the aluminum nitrate solution is 1：(0.5~2)；Step (2)
Described in the mass ratio of graphene oxide, aluminum nitrate and amount of urea that contains in graphene oxide water solution be 1：(50~
80)：(30~40)；A concentration of 0.3~0.8mg/mL of graphene oxide water solution in step (2)；And/or institute in step (3)
The mass ratio for stating hercynite and hydrated alumina-redox graphene composite material dosage is 1：(0.3~3).
The present invention provides iron aluminium point crystalline substance made from the preparation method by the present invention described in first aspect in second aspect
Stone composite material.
The present invention provides a kind of preparation method of hercynite composite material modified glassy carbon electrode, institute in the third aspect
The method of stating includes the following steps：
(a) with dimethylformamide that hercynite made from preparation method of the present invention described in first aspect is compound
Material is configured to the solution containing hercynite composite material；With
(b) solution containing hercynite composite material that step (a) is prepared is added dropwise to the surface of glass-carbon electrode, so
After dry, hercynite composite material modified glassy carbon electrode is made.
Preferably, a concentration of 0.4~0.8mg/ for the solution containing hercynite composite material that step (a) is prepared
mL。
Preferably, the glass-carbon electrode is pretreated glass-carbon electrode, and the pre-treatment step of the glass-carbon electrode is：It will
Glass-carbon electrode uses grain size to be processed by shot blasting for the aluminium oxide powder that 0.2~0.4 μm is 40~60nm with grain size successively, so
It is ultrasonically treated in second alcohol and water, is finally dried in a nitrogen atmosphere successively afterwards, obtain pretreated glass-carbon electrode.
The present invention provides hercynite made from the preparation method by the present invention described in third face in fourth aspect
Composite material modified glassy carbon electrode.
The present invention provides a kind of hercynite composite material modified glassy carbon electrode in detecting solution at the 5th aspect
Application in heavy metal ion, the method are multiple using hercynite made from the preparation method of the invention described in third face
Condensation material modified glassy carbon electrode detects the heavy metal ion in solution as working electrode, using anodic stripping voltammetry.
The present invention at least has the advantages that compared with prior art：
1, the present invention uses hercynite (FeAl2O4) it is primary raw material, select hydrated alumina (γ-AlOOH) modified
Redox graphene (rGO) to prevent redox graphene from assembling and increase the active site of redox graphene,
Hydrated alumina-redox graphene composite material (AlOOH-rGO) is set to become the carrier material of hercynite particle,
Preparation has synthesized hercynite composite material (FeAl2O4-AlOOH-rGO)。
2, the present invention uses cheap ferric nitrate, aluminum nitrate and urea etc. to be prepared for a kind of novel iron aluminium point crystalline substance for raw material
Stone composite material, manufacturing cost is low, preparation process it is simple and free from environmental pollution, it can be achieved that hercynite composite material batch
Production.
3, hercynite composite material prepared by the present invention can be by divalent metal ion (M2+Ion) it is reduced into its element
State, can form closed circuit in the test of electrochemistry, and hercynite composite material is examined as electrode material in electrochemistry
There is important application value in check weighing metal ion.
4, the hercynite composite material modified glassy carbon electrode for preparing of the present invention can quickly detect the metal in solution from
Son, such as hercynite composite material modified glassy carbon electrode is to divalent cadmium ion (Cd in solution2+) and lead (II) ion (Pb2 +) there is larger detection range (Cd2+Linear concentration detection range be 0.5~9.0 μm of ol/L, Pb2+Linear concentration detection
Ranging from 0.25~4.5 μm of ol/L), and Cd can be reduced2+And Pb2+Detection limit (Cd2+Detection be limited to 9.6nmol/L, Pb2+'s
Detection is limited to 3.3nmol/L), and in the trivalent bismuth ion (Bi that optimization concentration is added3+) under conditions of can be achieved Cd2+And Pb2+'s
It detects simultaneously.
5, hercynite composite material modified glassy carbon electrode prepared by the present invention is quickly being examined as electrochemical sensor
There is in survey solution in heavy metal ion high sensitivity, at low cost, detection to limit, and low, detection range is wide, anti-interference is good, reproducibility
The advantages that good and stability is good；Hercynite composite material modified glassy carbon electrode improves detection of heavy metal ion sensor
Comprehensive performance can be the detection and analysis method that heavy metal ion is provided with effect.
Description of the drawings
Fig. 1 is the preparation flow figure of the present invention.
Fig. 2 is hercynite, hydrated alumina-redox graphene composite material and iron aluminium point prepared by the present invention
The scanning electron microscope and transmission electron microscope figure of spar composite material.(a) and (b) is respectively hercynite in figure
Scanning electron microscope diagram and transmission electron microscope figure；(c) and (d) is respectively hydrated alumina-reduction-oxidation graphite in figure
The scanning electron microscope diagram and transmission electron microscope figure of alkene composite material；(e) and figure (f) are respectively hercynite in figure
The scanning electron microscope diagram and transmission electron microscope figure of composite material.
Fig. 3 is hercynite, hydrated alumina-redox graphene composite material and iron aluminium point prepared by the present invention
The X-ray diffraction spectrogram of spar composite material.2 θ are expressed as twice of the angle of diffraction in figure, and unit is degree (°).
Fig. 4 is hercynite composite material modified glassy carbon electrode, exposed glass-carbon electrode and water prepared by the present invention
It closes aluminium oxide-redox graphene composite material modified glassy carbon electrode and passes through cyclic voltammetry, electrochemical AC impedance respectively
The Electrochemical Characterization figure that spectrum analysis and Square wave anodic stripping voltammetry method carry out.(a) is cyclic voltammogram in figure；In figure (b)
For electrochemical alternate impedance spectrum figure (the complex number plane figure of impedance), using the real part of impedance as abscissa (Z '), unit ohm,
Using the imaginary part of impedance as ordinate (Z ＂), unit ohm；(c) is square wave anodic stripping voltammetry figure in figure.
Fig. 5 is hercynite composite material modified glassy carbon electrode prepared by the present invention while detecting Cd2+And Pb2+To branch
Hold electrolyte, pH, deposition potential, sedimentation time, Bi3+The condition optimizing figure of concentration.(a) is that the condition of supporting electrolyte is excellent in figure
Change figure；(b) is the condition optimizing figure of pH value in figure；(c) is the condition optimizing figure of deposition potential in figure；When (d) is deposition in figure
Between condition optimizing figure；(e) is Bi in figure3+The condition optimizing figure of concentration.
Fig. 6 be the hercynite composite material modified glassy carbon electrode for preparing of the present invention with optimal conditions, detect simultaneously
Cd2+And Pb2+Square wave anodic stripping voltammetry figure.
Fig. 7 is the hercynite composite material modified glassy carbon electrode of the invention prepared with optimal conditions while detecting
Cd2+And Pb2+When, Cd2+And Pb2+Dissolution peak current and concentration linear relationship chart.(a) is Cd in figure2+Dissolution peak current
With Cd2+Concentration linear relationship chart；(b) is Pb in figure2+Dissolution peak current and Pb2+Concentration linear relationship chart.
Fig. 8 is the result of the anti-interference of hercynite composite material modified glassy carbon electrode prepared by the evaluation present invention
Figure.
Fig. 9 be the hercynite composite material modified glassy carbon electrode for preparing of the present invention with optimal conditions continuous 10 times it is same
When detect Cd2+And Pb2+Square wave anodic stripping voltammetry figure.
Figure 10 is the reproducibility and stability of hercynite composite material modified glassy carbon electrode prepared by the evaluation present invention
Result figure.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiment of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of the every other embodiment that is obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation method of hercynite composite material in first aspect, and the method includes such as
Lower step：
(1) iron nitrate solution and aluminum nitrate solution are mixed, obtains the first mixed liquor, then first mixed liquor exists
It is stirred under the conditions of 60~80 DEG C (such as 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C), obtains iron-aluminium oxide xerogel, then by institute
It states iron-aluminium oxide xerogel grind into powder to be calcined later, hercynite is made；
(2) aluminum nitrate and urea are uniformly mixed with graphene oxide water solution, obtain the second mixed liquor, it then will be described
Second mixed liquor keeps the temperature 9 under the conditions of 150~200 DEG C (such as 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C)~
12h (such as 9,9.5,10,10.5,11,11.5 or 12h) and then process centrifugal treating remove liquid, and aqua oxidation is made
Aluminium-redox graphene composite material；With
(3) with ethyl alcohol by hydrated alumina-reduction-oxidation made from hercynite made from step (1) and step (2)
Graphene composite material is uniformly mixed, and obtains third mixed liquor, then by the third mixed liquor at 60~100 DEG C (such as 60
DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C) under the conditions of dry 10~16h (such as 10,11,12,13,14,15 or 16h), iron is made
Aluminate composite material.
According to some preferred embodiments, the method further includes that step (1) is made before carrying out step (3)
Hercynite carry out wet ball grinding and dry step successively：The time of the wet ball grinding be 18~30h (such as 18,
19,20,21,22,23,24,25,26,27,28,29 or 30h).
According to some preferred embodiments, the method further includes that step (2) are made before carrying out step (3)
Hydrated alumina-redox graphene composite material step for being washed and dried successively.
According to some preferred embodiments, the temperature calcined in step (1) be 600~900 DEG C (such as 600 DEG C, 700
DEG C, 800 DEG C or 900 DEG C), time of calcining is 1~3h (such as 1,1.5,2,2.5 or 3h)；Ferric nitrate is molten described in step (1)
Liquid is iron nitrate aqueous solution and/or aluminum nitrate solution is aluminum nitrate aqueous solution, and the ferric nitrate is preferably Fe(NO3)39H2O
(Fe(NO3)3·9H2O), the aluminum nitrate is preferably ANN aluminium nitrate nonahydrate (Al (NO3)3·9H2O)；Nitric acid described in step (1)
The mass ratio of the ferric nitrate contained in ferrous solution and the aluminum nitrate contained in the aluminum nitrate solution is 1：(0.5~2) (such as 1:
0.5、1:0.8、1:1 or 1:2)；The graphene oxide that contains in graphene oxide water solution described in step (2), aluminum nitrate and
The mass ratio of amount of urea is 1：(50~80)：(30~40) (such as 1:50:30、1:50:35、1:50:40、1:60:30、1:
60:35、1:60:40、1:70:30、1:70:35、1:70:40、1:80:30、1:80:35 or 1:80:40)；Oxidation in step (2)
A concentration of 0.3~0.8mg/mL (such as 0.3,0.4,0.5,0.6,0.7 or 0.8mg/mL) of graphene aqueous solution；The oxidation
The dosage of graphene aqueous solution is preferably 30~60mL (such as 30,40,50 or 60mL)；And/or the point of iron aluminium described in step (3)
Spar and the mass ratio of hydrated alumina-redox graphene composite material dosage are 1：(0.3~3) (such as 1:0.3、1:
0.5、1:0.8、1:1、1:2 or 1:3).
According to some, more specifically embodiment, the preparation of hercynite composite material include：Use nine hydration nitre
Two kinds of precursors are dissolved in water (such as deionized water) and are stirred at room temperature as precursor by sour iron and ANN aluminium nitrate nonahydrate respectively
30 minutes, iron nitrate aqueous solution and aluminum nitrate aqueous solution are respectively obtained, the iron nitrate aqueous solution and aluminum nitrate aqueous solution are mixed
Close, obtain the first mixed liquor, then by first mixed liquor temperature be mixed on 70 DEG C of hot plate a few hours (such as
Can be 6h), obtain stable iron-aluminium oxide xerogel, then by the iron-aluminium oxide xerogel be ground to powder and
It is calcined under the conditions of 800 DEG C, it is finally for 24 hours and dry by wet ball grinding successively, obtain hercynite particle (FeAl2O4Particle).
A certain proportion of ANN aluminium nitrate nonahydrate and urea is taken to be dissolved in a concentration of 0.5mg/mL graphene oxide water solutions of 40mL, then
At 25 DEG C after ultrasound 1h (uniformly mixed), the second mixed liquor is obtained, second mixed liquor is then transferred to 50mL high pressures
In kettle, (heat preservation) 12h is heated at 180 DEG C, removes liquid using centrifugal treating, solid matter is obtained from the second mixed liquor
Hydrated alumina-redox graphene composite material (AlOOH-rGO), is finally washed three times with absolute ethyl alcohol, and at 60 DEG C
It is dry in vacuum drying oven.Hercynite and hydrated alumina-redox graphene composite material mixing is taken to be dissolved in ethyl alcohol (example
Such as absolute ethyl alcohol, and chosen according to the dosage of hercynite and hydrated alumina-redox graphene composite material anhydrous
The dosage of ethyl alcohol be 80~200mL) in, by ultrasound and magnetic agitation (every 20min alternately ultrasound and magnetic agitation,
The process is repeated 3 times) uniformly mixed third mixed liquor is obtained, it is then that third mixed liquor is dry in 80 DEG C of vacuum drying oven
12 hours, obtain hercynite composite material (FeAl2O4-AlOOH-rGO)。
The present invention provides iron aluminium point crystalline substance made from the preparation method by the present invention described in first aspect in second aspect
Stone composite material.
The present invention provides a kind of preparation method of hercynite composite material modified glassy carbon electrode, institute in the third aspect
The method of stating includes the following steps：
(a) use dimethylformamide (DMF) that iron aluminium point made from preparation method of the present invention described in first aspect is brilliant
Stone composite material is configured to the solution containing hercynite composite material；With
(b) solution containing hercynite composite material that step (a) is prepared is added dropwise to the surface of glass-carbon electrode, so
After dry, hercynite composite material modified glassy carbon electrode is made.
According to some preferred embodiments, step (a) prepare the solution containing hercynite composite material it is dense
Degree is 0.4~0.8mg/mL (such as 0.4,0.5,0.6,0.7 or 0.8mg/mL)；And/or dropwise addition contains iron in step (b)
The dosage of the solution of aluminate composite material is 4~8 μ L (such as 4,5,6,7 or 8 μ L).
According to some preferred embodiments, the glass-carbon electrode is pretreated glass-carbon electrode, the glass-carbon electrode
Pre-treatment step be：Glass-carbon electrode is used successively grain size be for 0.2~0.4 μm (such as 0.2,0.3 or 0.4 μm) and grain size
The aluminium oxide powder of 40~60nm (such as 40,50 or 60nm) is processed by shot blasting, is then carried out in second alcohol and water successively
It is ultrasonically treated, finally dries in a nitrogen atmosphere, obtain pretreated glass-carbon electrode.
The present invention does not require the size of glass-carbon electrode particularly, the glass-carbon electrode of preferably a diameter of 3mm, step
(b) dosage of the solution containing hercynite composite material of dropwise addition is preferably 4~8 μ L (such as 4,5,6,7 or 8 μ in
L)。
According to some, more specifically embodiment, the preparation of the hercynite composite modified glassy carbon electrode include：
By exposed glass-carbon electrode (a diameter of 3mm) respectively with 0.3 μm and the aluminium oxide powder (Al of 50nm2O3Slurry) carry out surface
Polishing treatment is fully rinsed with deionized water between each polishing treatment step, is then spent successively to form mirror like surface
Ionized water and alcohol are ultrasonically treated 0.5~3min (such as 30s, 1min, 2min or 3min), finally dry in a nitrogen atmosphere
(drying) obtains pretreated glass-carbon electrode (clean glass-carbon electrode)；It is with 20mL dimethylformamides that 10mg iron aluminium is sharp
Spar composite material is configured to the solution containing hercynite composite material of a concentration of 0.5mg/mL；Take 5 μ L's to contain iron
The surface for being dispersed to pretreated glass-carbon electrode is added dropwise in the solution of aluminate composite material, and drying is (dry at room temperature
It is dry), hercynite composite modified glassy carbon electrode is made.
The present invention provides iron aluminium point crystalline substance made from the preparation method by the present invention described in the third aspect in fourth aspect
Stone composite material modified glassy carbon electrode.
The present invention provides a kind of hercynite composite material modified glassy carbon electrode in detecting solution at the 5th aspect
Application in heavy metal ion, the method is using hercynite made from the preparation method of the invention described in the third aspect
Composite material modified glassy carbon electrode detects the heavy metal ion (example in solution as working electrode, using anodic stripping voltammetry
Such as Square wave anodic stripping voltammetry method is used to detect divalent cadmium ion and lead (II) ion in solution simultaneously).
It illustrates, hercynite is denoted as FeAl by the present invention2O4, hydrated alumina (boehmite) is denoted as
AlOOH, redox graphene are denoted as rGO, hydrated alumina-redox graphene composite material and are denoted as AlOOH-rGO, iron
Aluminium point metal and stone composite material is denoted as FeAl2O4- AlOOH-rGO, glass-carbon electrode are denoted as GCE, divalent cadmium ion is denoted as Cd2+Or Cd
(II), lead (II) ion is denoted as Pb2+Or Pb (II), trivalent bismuth ion are denoted as Bi3+, barium ions be denoted as Ba2+, calcium ion be denoted as Ca2 +, potassium ion be denoted as K+, magnesium ion be denoted as Mg2+It is denoted as Zn with zinc ion2+.The present invention is by unit mol/L, mmol/L, μ of concentration
Mol/L and nmol/L be also denoted as respectively M, mM, μM and nM.
Embodiment
It hereafter will be by way of example to hercynite composite material in the present invention and hercynite composite material
Modified glassy carbon electrode further illustrates, but protection scope of the present invention is not limited to these embodiments.
The present invention uses X-ray diffraction (XRD) collection of illustrative plates, scanning electron microscope (SEM) and transmission electron microscope (TEM)
The structure and pattern of material are characterized.In the PW1710 instruments for radiating (40KV, 20mA, λ=1.5406) with CuK α
Upper acquisition XRD spectrum.SEM image is shot by FEI Quanta 200FEG field emission scanning electron microscopes, passes through JEM-
2010HR transmission electron microscopes shoot TEM image.
Electrochemical measurement of the present invention includes cyclic voltammetry (CV), electrochemical impedance spectrum analysis (EIS) and Anodic Stripping volt
Peace method (ASV) (such as Square wave anodic stripping voltammetry method (SWASV)) is in CHI 760E electrochemical workstation (manufacturers：Morning Hua Yi
Device Co., Ltd；Grown place：Chinese Shanghai) it is carried out using conventional three-electrode system.Three-electrode system includes：Using exposed glass
Carbon electrode or the glassy carbon electrode of modification are used as working electrode, platinum electrode to electrode and silver/silver chloride electrode (Ag/
AgCl electrodes) it is used as reference electrode.
Electrochemical measurement：Cyclic voltammetry and electrochemical impedance spectrum analysis are with 100mVs-1Sweep speed a concentration of
The potassium ferricyanide of 5mmol/L is carried out with the mixed solution of the potassium chloride of a concentration of 0.1mol/L.Electrochemical impedance spectrum analysis is set
The parameter set is：Frequency range is 10-1~105Hz；DC potential is 180mV；AC amplitude is 5mV；Increment current potential is 4mV.
Square wave anodic stripping voltammetry method (SWASV) observes the electrification of hercynite composite material modified glassy carbon electrode with optimal conditions
Scholarship and moral conduct is：By restoring Cd in the NaAc_HAc buffer solution (HAc-NaAc) of 0.1mol/L, pH=5.52+And Pb2+,
And 240s is deposited under the deposition potential of -0.7V, the potential range of the Anodic Stripping of metal ion electro-deposition -1.0 to 0.2V
Interior progress, before entering next cycle, the desorption current potential for carrying out 240s is 0.7V, to remove remaining metal；The present invention
Anti-interference, reproducibility and the stability test experiment of hercynite composite material modified glassy carbon electrode use identical optimization
Condition.
Embodiment 1：The preparation of hercynite composite material and hercynite composite material modified glassy carbon electrode is tested.
1. the preparation of hercynite composite material：It, will using Fe(NO3)39H2O and ANN aluminium nitrate nonahydrate as precursor
Two kinds of precursors are dissolved in water (such as deionized water) and are stirred at room temperature 30 minutes respectively, respectively obtain iron nitrate aqueous solution and
Nine contained in aluminum nitrate aqueous solution, the Fe(NO3)39H2O contained in the iron nitrate aqueous solution and the aluminum nitrate aqueous solution
The mass ratio of nitric hydrate aluminium is 1:1, the iron nitrate aqueous solution and aluminum nitrate aqueous solution are mixed, the first mixed liquor is obtained,
Then a few hours are mixed on the hot plate that temperature is 70 DEG C in first mixed liquor, it is dry obtains stable iron-aluminium oxide
Gel, then the iron-aluminium oxide xerogel is ground to powder and is calcined under the conditions of 800 DEG C, finally pass through wet method ball successively
Mill is for 24 hours and dry, obtains hercynite particle.ANN aluminium nitrate nonahydrate and urea is taken to be dissolved in a concentration of 0.5mg/mL of 40mL
Graphene oxide water solution (the quality of the graphene oxide, ANN aluminium nitrate nonahydrate and the urea that contain in graphene oxide water solution
Than being 1:60:30), then at 25 DEG C after ultrasound 1h (uniformly mixed), the second mixed liquor is obtained, is then mixed described second
Liquid is transferred in 50mL autoclaves, and (heat preservation) 12h is heated at 180 DEG C, and liquid is removed using centrifugal treating, from the second mixing
Solid matter hydrated alumina-redox graphene composite material is obtained in liquid, is finally washed three times with absolute ethyl alcohol, and
It is dry in 60 DEG C of vacuum drying ovens.It is 1 to take mass ratio:1 hercynite and hydrated alumina-redox graphene composite wood
Material mixing is dissolved in 100mL absolute ethyl alcohols, by ultrasound and magnetic agitation (every 20min alternately ultrasound and magnetic agitation,
The process is repeated 3 times) uniformly mixed third mixed liquor is obtained, it is then that third mixed liquor is dry in 80 DEG C of vacuum drying oven
12 hours, obtain hercynite composite material.
2. the preparation of hercynite composite material modified glassy carbon electrode：By exposed glass-carbon electrode (a diameter of 3mm) point
Not with 0.3 μm and the aluminium oxide powder (Al of 50nm2O3Slurry) carry out surface polishing treatment to form mirror like surface, each
It is fully rinsed with deionized water between polishing treatment step, then deionized water and alcohol is used to be ultrasonically treated 30s successively, finally existed
It is dried under nitrogen atmosphere, obtains pretreated glass-carbon electrode；It is with 20mL dimethylformamides that 10mg hercynites is compound
Material is configured to the solution containing hercynite composite material of a concentration of 0.5mg/mL；Take 5 μ L's to contain hercynite
The surface for being dispersed to pretreated glass-carbon electrode is added dropwise in the solution of composite material, and dries at room temperature, and it is brilliant that iron aluminium point is made
Stone composite material modified glassy carbon electrode.
The present embodiment is compound to hercynite by scanning electron microscope (SEM) and transmission electron microscope (TEM)
Material has carried out the characterization of surface topography, as shown in Figure 2.Fig. 2 (a) shows FeAl2O4Form, it can be found that FeAl2O4Particle
Shape it is irregular and uneven due to aggregation；Fig. 2 (b) is shown corresponding to FeAl2O4(standard JCPDS No.34-
0192) distance between the surface of (220) crystal face is 0.28nm.Fig. 2 (c) shows that AlOOH nanometer sheets are inserted into the nanometer sheet of rGO
In, and rGO is the typical individual layer nanometer sheet structure with fold, Fig. 2 (d) can clearly be observed that be repaiied in rGO nanometer sheets
Thin AlOOH nanometer sheets have been adornd, the segregation of rGO nanometer sheets is effectively prevented.Fig. 2 (e) is it can be seen that many FeAl2O4Particle
The surfaces AlOOH-rGO are distributed in, Fig. 2 (f) shows FeAl2O4Particle is uniformly distributed on the surfaces AlOOH-rGO.
Structural characterization characterization is carried out to hercynite composite material by X-ray diffraction spectrogram (XRD), such as Fig. 3 institutes
Show.For FeAl2O4XRD spectra, characteristic diffraction peak from left to right is corresponding in turn in (220), (311), (400), (422),
(533), (620) and (440) crystal face, FeAl2O4XRD spectra in without display iron (Fe) or alundum (Al2O3) (Al2O3) it is miscellaneous
Mass peak.The characteristic peak of graphene oxide is not observed in the XRD spectra of the AlOOH-rGO of synthesis, shows in the hydro-thermal reaction phase
Between graphene oxide all Restore Alls be redox graphene, and do not go out corresponding to the diffraction maximum of (002) crystal face of rGO
Existing, this is because rGO pieces have been modified AlOOH nanocrystals and removed, this is also indicated that, is effectively prevented in AlOOH-rGO
The segregation of rGO nanometer sheets, therefore, the rGO nanometer sheets in AlOOH-rGO can keep its high activity surface product and electric conductivity.For
The FeAl of synthesis2O4The XRD diagram of-AlOOH-rGO, characteristic peak respectively with FeAl2O4The feature peak match of particle and AlOOH-rGO,
This, which is also indicated that, successfully prepares hercynite composite material (FeAl2O4-AlOOH-rGO)。
The present embodiment is respectively with hercynite composite material modified glassy carbon electrode (FeAl2O4- AlOOH-rGO/GCE), it is naked
The glass-carbon electrode (GCE) and hydrated alumina of dew-redox graphene composite material modified glassy carbon electrode (AlOOH-rGO/
GCE) it is used as working electrode using cyclic voltammetry (CV), electrochemical alternate impedance spectrum analysis (EIS) and square wave Anodic Stripping volt
Peace method (SWASV) has carried out the electrochemical Characterization of three kinds of working electrodes, and the results are shown in Figure 4.
The result figure of cyclic voltammetry is it is observed that multiple with hydrated alumina-redox graphene in Fig. 4 (a)
When condensation material modified glassy carbon electrode is as working electrode, Metal Ions Cd2+And Pb2+Dissolution peak current increase, and cathode peak and
Peak potential difference between anode peak reduces, this shows hydrated alumina-redox graphene composite material modified glassy carbon electrode
It improves to Cd2+And Pb2+Electrochemical catalysis performance；Hercynite composite material modified glassy carbon electrode compares aqua oxidation
Aluminium-redox graphene composite material modified glassy carbon electrode, Cd2+And Pb2+Dissolution peak current further increase, the result
It is attributed to FeAl2O4Necessary pathway can be provided at the electrode surface, and there is better electrochemical behavior, promoted
Make the Fe (CN) contained in potassium ferricyanide solution6 3-/4-Electrode surface is diffused into carry out electron exchange and unblock.Fig. 4's (b)
Electrochemical alternate impedance spectrum figure further confirms that the interfacial property of different materials modified electrode, in general, electrochemical ac
Impedance consists of two parts, i.e. semi-circular portions and straight line portion.From the semicircle of upper frequency, we can obtain electronics transfer electricity
Resistance, low frequency linear segment correspond to diffusion process, from Fig. 4 (b) it can be seen that hercynite composite material modified glassy carbon electrode
The diameters of semi-circular portions be substantially reduced, show the reduction of electronics transfer resistance.Using Square wave anodic stripping voltammetry method containing dense
Spend the Cd of 0.5 μm of ol/L2+With the Pb of 0.5 μm of ol/L2+0.1mol/L, pH be 5.5 Acetic acid-sodium acetate buffer solution in, and vinegar
Contain Bi in acid-sodium-acetate buffer3+A concentration of 3 μm of ol/L under conditions of, -1.0 to -0.4V potential range, deposition
Potential is when carrying out the deposition process of 150s under -0.7V, from Fig. 4 (c) as can be seen that exposed glass-carbon electrode is as working electrode
When observe two very weak dissolution peaks, hydrated alumina-redox graphene composite material modified glassy carbon electrode conduct
Two stronger peaks are obtained when working electrode, it may be possible to the electric conductivity and aqua oxidation having had due to redox graphene
The aluminium adsorption capacity big to heavy metal ion, under the same conditions, hercynite composite material modified glassy carbon electrode is as work
When making electrode, Cd2+And Pb2+More sharp and higher dissolution peak electricity can be obtained at the current potential of -0.78 and -0.58V respectively
Stream, hercynite composite material modified glassy carbon electrode is to Cd2+And Pb2+Dissolution peak current response increase may be attributed to
FeAl2O4Specific conductivity energy, the good adsorption ability of AlOOH, rGO bigger serface and Bi3+It is easy to and heavy metal
Form the ability of alloy.
These results indicate that the chemical property of hercynite composite material modified glassy carbon electrode is better than exposed glass
Carbon electrode and hydrated alumina-redox graphene composite material modified glassy carbon electrode, the modification of hercynite composite material
Glass-carbon electrode is suitable for while measuring Cd2+And Pb2+。
Following embodiments are all made of the hercynite composite material modified glassy carbon electrode of the preparation of embodiment 1 as work electricity
Pole.
Embodiment 2：Hercynite composite material modified glassy carbon electrode detects the condition optimizing experiment before heavy metal ion.
In order to obtain hercynite composite material modified glassy carbon electrode while measure Cd2+And Pb2+High current response,
Have studied experiment parameter (supporting electrolyte, pH value, deposition potential, sedimentation time and Bi3+Concentration) influence, obtained support
Electrolyte, pH value, deposition potential, sedimentation time and addition Bi3+The condition optimizing figure of concentration is as shown in Figure 5.
Supporting electrolyte：The Cd containing a concentration of 0.5 μm of ol/L is evaluated by changing supporting electrolyte2+With 0.5 μm of ol/
The Pb of L2+Mixed solution anodic stripping voltammetry reaction.Fig. 5 (a) is that hercynite composite material modified glassy carbon electrode exists
NaAc_HAc buffer solution (NaAc-HAc), phosphate buffer solution (PBS) and the ammonium chloride that 0.1mol/L and pH value are 5.0
Buffer solution (NH4Cl-NH4OH to Cd in)2+And Pb2+Anodic stripping voltammetry figure, be not observed in phosphate buffer solution
Apparent dissolution peak current, observes the dissolution peak of reduced-current response in ammonium chloride buffer solution, slow in Acetic acid-sodium acetate
It rushes in solution, observes the dissolution peak of higher current-responsive, and show specific Cd2+And Pb2+Anodic stripping voltammetry peak
Shape.Therefore, a concentration of 0.1mol/L NaAc_HAc buffer solutions are used in condition optimizing below experiment.
PH value：Fig. 5 (b) is for pH to containing in 0.1mol/L NaAc_HAc buffer solutions in 3.0~7.0 ranges
The Cd of 0.5 μm of ol/L2+With the Pb of 0.5 μm of ol/L2+Dissolution peak current response, as can be observed from Figure, Cd2+And Pb2+It is molten
Go out peak current first to increase as pH value increases, maximum current value occurs when pH is 5.5, and pH is more than dissolution peak electricity after 5.5
Rheology is low.This is because when pH is too low, hercynite composite material (FeAl2O4- AlOOH-rGO) stability will be broken
It is bad, when pH value is higher than 5.5, Cd is reduced since the hydrolysis of metal ion can reduce2+And Pb2+Deposition.Therefore in item below
The NaAc_HAc buffer solution for the use of 0.1mol/L, pH being 5.5 in piece optimization experiment.
Deposition potential：In the Cd containing 0.5 μm of ol/L2+With the Pb of 0.5 μm of ol/L2+0.1mol/L pH be 5.5 vinegar
It is heavy come the difference for testing -1.1 to -0.4V potential range by Square wave anodic stripping voltammetry method in acid-sodium acetate buffer
The influence of product potential.From Fig. 5 (c) as can be seen that when current potential be higher than -0.7V when, dissolution peak current with the reduction of deposition potential and
Increase, when current potential is less than -0.7V, dissolution peak current reduces Cd2+And Pb2+Dissolution peak current reach under the current potential of -0.7V
Maximum value.Therefore, deposition potential is selected as -0.7V.
Sedimentation time：In the Cd containing 0.5 μm of ol/L2+With the Pb of 0.5 μm of ol/L2+0.1mol/L pH be 5.5 vinegar
The influence of 60 to 420s different sedimentation times is tested in acid-sodium acetate buffer by Square wave anodic stripping voltammetry method.
Shown in Fig. 5 (d), when deposited between when being less than 240s, with the increase of sedimentation time, Cd2+And Pb2+Dissolution peak current be in line
Property increase, when deposited between be higher than 240s when dissolution peak current slowly rise, this shows electrode surface by Cd2+And Pb2+It is gradually full
With.The increase of sedimentation time not only improves sensitivity, also upper limit of detection can be caused to reduce since the surface of modified electrode is saturated.Cause
This selects 240s as the sedimentation time of following experiment to realize lower detection limit and broader response range.
Bi3+Concentration：It is well known that bismuth film electrode has highly sensitive and repeatability, because it tends to and heavy metal shape
At alloy, this readily facilitates nucleation process during the pre-concentration of heavy metal ion.Therefore, the dissolution peak electricity in order to obtain
Stream response selects the Bi of concentration appropriate3+It is very necessary.As shown in Fig. 5 (e), in no Bi3+In the case of obtain very
Weak dissolution peak current, and in addition Bi3+When dissolution peak current be obviously improved.When μm ol/L changes concentration from 0 to 3.0,
Peak point current increases sharply.However, with Bi3+Concentration further increase, dissolution peak current is only slight to be increased.Therefore, Bi3 +Concentration optium concentration be selected as 3.0 μm of ol/L.
The present embodiment show that the experiment parameter of optimization is：The vinegar that supporting electrolyte is a concentration of 0.1mol/L and pH is 5.5
Acid-sodium acetate buffer (NaAc-HAc buffer solutions), deposition potential are -0.7V, sedimentation time 240s, Bi3+A concentration of 3
μmol/L。
Embodiment 3：Hercynite composite material modified glassy carbon electrode detects the experiment of heavy metal ion.
It is electric using hercynite composite material modified glassy carbon electrode as work on the basis of 2 Optimal Parameters of embodiment
Pole measures Cd using Square wave anodic stripping voltammetry method2+And Pb2+Solution in the presence of common, while measuring Cd2+And Pb2+Changing
Current-responsive when concentration (concentration increased continuously), the results are shown in Figure 6.Cd as can be seen from Figure 62+And Pb2+Dissolution peak electricity
Position respectively appears in -0.75V and -0.54V, and the dissolution peak current of two kinds of analysis ions increases with the increase of its concentration.
Cd2+And Pb2+Dissolution peak current and concentration it is in a linear relationship, as shown in Figure 7.
Cd in solution2+Current value (I) and Cd2+The linear relationship curve of concentration (C) be：I (μ A)=1.70+1.49C
(μM)(R2=0.993), Cd2+Linear concentration detection range be 0.5~9.0 μm of ol/L；Pb in solution2+Current value (I) with
Pb2+The linear relationship curve of concentration (C) be：I (μ A)=0.95+4.29C (μM) (R2=0.982), Pb2+Linear concentration inspection
Survey ranging from 0.25~4.5 μm of ol/L；Wherein R2Indicate related coefficient.
Cd is calculated by 3 times of standard deviations (3 σ methods) in the present embodiment2+Detection be limited to 9.6nmol/L, Pb2+'s
Detection is limited to 3.3nmol/L.
Compared with the electrode of other materials modification, hercynite composite material modified glassy carbon electrode detects Cd at the same time2+
And Pb2+When, lower detection limit can be obtained and wide linear detection range, these results also indicate that hercynite composite wood
Material modified glassy carbon electrode can be successfully applied to Cd2+And Pb2+While measure.
Embodiment 4：Anti-interference, reproducibility and the stability test of hercynite composite material modified glassy carbon electrode are real
It tests.
The present embodiment carries out on the basis of 2 Optimal Parameters of embodiment.
In order to evaluate the anti-interference of hercynite composite material modified glassy carbon electrode, with hercynite composite material
Modified glassy carbon electrode is working electrode, in a concentration of 0.6 μM of Cd2+With a concentration of 0.6 μM of Pb2+Under concurrent conditions, add respectively
Enter the Ba that concentration is 3 μM (concentration of 5 times of detection ion)2+、Ca2+、K+、Mg2+And Zn2+After ion, Cd2+And Pb2+Dissolution
Peak current it is almost unchanged, respectively as shown in Fig. 8 (a) and Fig. 8 (b), illustrate other ion pairs while detecting Cd2+And Pb2+It is dry
Disturbing reaction can be ignored, and illustrate hercynite composite material modified glassy carbon electrode to Cd2+And Pb2+Adsorption capacity it is good, choosing
Selecting property is good.The ordinate of Fig. 8 (a) and (b) indicate that the Cd after other ions is added respectively2+And Pb2+Dissolution peak current (Is) with
It is added without the Cd of other ions2+And Pb2+Dissolution peak initial current value (I0) ratio, be denoted as Is/I0；And it indicates not add with 1
Enter other ions, indicate to be individually added into Ba with 2,3,4,5 and 62+、Ca2+、K+、Mg2+And Zn2+Result afterwards.
In order to evaluate hercynite composite material modified glassy carbon electrode to Cd2+And Pb2+The reproducibility of testing result and steady
Qualitative, the present embodiment is to the Cd containing a concentration of 0.6 μm of ol/L2+With the Pb of a concentration of 0.6 μm of ol/L2+Solution carry out it is continuous
10 Cd2+And Pb2+Deposition and dissolution (i.e. by Cd2+And Pb2+First be reduced to Cd and Pb be deposited on electrode surface, reoxidize for
Cd2+And Pb2+Dissolve out in solution), each Cd is measured using Square wave anodic stripping voltammetry method2+And Pb2+It is corresponding molten to dissolve out peak
Go out electric current, it is found that this 10 times dissolution peak currents are nearly constant (highly repeatable dissolution peak current), as shown in Figure 9.Wherein this
10 Cd2+And Pb2+The corresponding electric current relative standard deviation (RSD) in dissolution peak is respectively 0.4% and 2.1%, dissolves out peak current
Change equal unobvious, as shown in Figure 10.
The result surface of the present embodiment shows hercynite composite material modified glassy carbon electrode while detecting Cd2+And Pb2+
With good anti-interference ability, reproducibility and stability.
Hercynite composite material modified glassy carbon electrode prepared by the present invention pair is detected simultaneously as electrochemical sensor
Cd2+And Pb2+Show excellent chemical property.Cd is realized with optimal conditions2+And Pb2+Wide detection range and phase
Lower detection is limited.In addition, hercynite composite material modified glassy carbon electrode is shown to Cd2+And Pb2+High selection
Property, and fabulous stability is provided in electrochemistry measures simultaneously, the present invention is in Electrochemical Detection toxic metal ions
Application field design new sensing material and provide potential material.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features；
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method of hercynite composite material, which is characterized in that described method includes following steps：
(1) iron nitrate solution and aluminum nitrate solution are mixed, obtain the first mixed liquor, then by first mixed liquor 60~
It is stirred under the conditions of 80 DEG C, obtains iron-aluminium oxide xerogel, then by the laggard of the iron-aluminium oxide xerogel grind into powder
Row calcining, is made hercynite；
(2) aluminum nitrate and urea are uniformly mixed with graphene oxide water solution, obtain the second mixed liquor, then by described second
Mixed liquor keeps the temperature 9~12h under the conditions of 150~200 DEG C and then removes liquid by centrifugal treating, and hydrated alumina-is made
Redox graphene composite material；With
(3) with ethyl alcohol by hydrated alumina-reduction-oxidation graphite made from hercynite made from step (1) and step (2)
Alkene composite material is uniformly mixed, and obtains third mixed liquor, then by the third mixed liquor dry 10 under the conditions of 60~100 DEG C
Hercynite composite material is made in~16h.
2. preparation method according to claim 1, which is characterized in that the method further includes before carrying out step (3)
Hercynite made from step (1) is subjected to wet ball grinding and dry step successively：The time of the wet ball grinding is 18
~30h.
3. preparation method according to claim 1, which is characterized in that the method further includes before carrying out step (3)
By the step that hydrated alumina-redox graphene composite material is washed and dried successively made from step (2).
4. preparation method according to claim 1, it is characterised in that：
The temperature calcined in step (1) is 600~900 DEG C, and the time of calcining is 1~3h；
Iron nitrate solution described in step (1) is iron nitrate aqueous solution and/or aluminum nitrate solution is aluminum nitrate aqueous solution；
The quality of the ferric nitrate contained in iron nitrate solution described in step (1) and the aluminum nitrate contained in the aluminum nitrate solution
Than being 1：(0.5~2)；
The mass ratio of the graphene oxide, aluminum nitrate and the amount of urea that contain in graphene oxide water solution described in step (2)
It is 1：(50~80)：(30~40)；
A concentration of 0.3~0.8mg/mL of graphene oxide water solution in step (2)；And/or
Hercynite described in step (3) and the mass ratio of hydrated alumina-redox graphene composite material dosage are
1：(0.3~3).
5. the hercynite composite material made from Claims 1-4 any one of them preparation method.
6. a kind of preparation method of hercynite composite material modified glassy carbon electrode, which is characterized in that the method includes such as
Lower step：
(a) with dimethylformamide by hercynite composite wood made from Claims 1-4 any one of them preparation method
Material is configured to the solution containing hercynite composite material；With
(b) solution containing hercynite composite material that step (a) is prepared is added dropwise to the surface of glass-carbon electrode, is then dried
It is dry, hercynite composite material modified glassy carbon electrode is made.
7. preparation method according to claim 6, it is characterised in that：
A concentration of 0.4~the 0.8mg/mL for the solution containing hercynite composite material that step (a) is prepared.
8. preparation method according to claim 6, which is characterized in that the glass-carbon electrode is that pretreated glass carbon is electric
The pre-treatment step of pole, the glass-carbon electrode is：
Glass-carbon electrode is used successively grain size be polished for the aluminium oxide powder that 0.2~0.4 μm is 40~60nm with grain size
Processing, is then ultrasonically treated in second alcohol and water, is finally dried in a nitrogen atmosphere, obtain pretreated glass carbon successively
Electrode.
9. the hercynite composite material modified glassy carbon electrode made from claim 6 to 8 any one of them preparation method.
10. a kind of application of hercynite composite material modified glassy carbon electrode in detecting solution in heavy metal ion, special
Sign is：The method is repaiied using hercynite composite material made from claim 6 to 8 any one of them preparation method
Glass-carbon electrode is adornd as working electrode, the heavy metal ion in solution is detected using anodic stripping voltammetry.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060284194A1 (en) * | 2005-06-20 | 2006-12-21 | Xerox Corporation | Imaging member |
| CN102430411A (en) * | 2011-09-13 | 2012-05-02 | 浙江省地质矿产研究所 | Hydrotalcite-like compound-spinel type ferrite composite material and preparation method thereof |
| CN104617251A (en) * | 2014-12-09 | 2015-05-13 | 贺灿辉 | Preparation method for graphene/spinel LiMn2O4 nanometer composite material |
-
2017
- 2017-12-29 CN CN201711481726.1A patent/CN108318551B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060284194A1 (en) * | 2005-06-20 | 2006-12-21 | Xerox Corporation | Imaging member |
| CN102430411A (en) * | 2011-09-13 | 2012-05-02 | 浙江省地质矿产研究所 | Hydrotalcite-like compound-spinel type ferrite composite material and preparation method thereof |
| CN104617251A (en) * | 2014-12-09 | 2015-05-13 | 贺灿辉 | Preparation method for graphene/spinel LiMn2O4 nanometer composite material |
Non-Patent Citations (3)
| Title |
|---|
| CHAO GAO 等: "AlOOH-Reduced Graphene Oxide Nanocomposites: One-Pot Hydrothermal Synthesis and Their Enhanced Electrochemical Activity for Heavy Metal Ions", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| NOÉ J. MORALES 等: "One-step chemical vapor deposition synthesis of magnetic CNT–hercynite (FeAl2O4) hybrids with good aqueous colloidal stability", 《CARBON》 * |
| YALE WU 等: "The effective determination of Cd(II) and Pb(II) simultaneously based on an aluminum silicon carbide-reduced graphene oxide nanocomposite electrode", 《ANALYST》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113480875A (en) * | 2021-07-27 | 2021-10-08 | 雷索新材料(苏州)有限公司 | Aluminum oxide modified graphene, graphene heat dissipation coating and preparation method thereof |
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