CN105938100A - New luminol cathode electrochemiluminescence excitation method based on ordered mesoporous carbon and polyaniline - Google Patents
New luminol cathode electrochemiluminescence excitation method based on ordered mesoporous carbon and polyaniline Download PDFInfo
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Abstract
The invention discloses a new luminol cathode electrochemiluminescence excitation method based on ordered mesoporous carbon and polyaniline. By cyclic voltammetry, an organic macromolecule polymer-polyaniline is polymerized to an inorganic carbon nanomaterial-ordered mesoporous carbon CMK-3 to form an organic-inorganic hybrid material composite film, and a glassy carbon electrode surface is modified with the composite film to construct a working electrode, a phosphoric acid buffer solution is used as an electrolyte buffer system, can excite luminol to obtain a sensitive and stable electrochemiluminescence radiation signal on a cathode electrochemiluminescence channel. Based on the sensing system, high-sensitive detection of hydrogen peroxide can be realized; the linear response range is 1.0*10<-9>-5.0*10<-5> mol/L. Through exciting luminol cathode electrochemiluminescence, high-sensitive detection of hydrogen peroxide is realized, and the method can be used for detection of actual samples, and has a certain application prospect in the biomedical field.
Description
Technical field
The invention belongs to electrochemiluminescence analysis technical field, be specifically related to a kind of based on ordered mesopore carbon and polyaniline
Luminol cathodic electrochromic chemiluminescence excites new method.
Background technology
In recent years, ordered mesoporous material (OMM) has been obtained for paying close attention to the most widely, wherein, and ordered mesopore carbon
(OCM) due to the electronic conductivity energy that the surprising characteristic of its uniqueness is the best, there is electrocatalysis characteristic, electron transfer can be accelerated
Speed, has the highest detection sensitivity, special selectivity, good stability, can reduce electricity Cucumber
Position, increases peak current, improves analytical performance, and have fabulous bio-compatibility, adjustable porous and bigger serface, will
For the fabrication method that the body plan offer of novel electrochemical sensor is new.
Conductive polymerized film such as polypyridine, polythiophene or polyaniline, containing conjugated electrons structure, started just to obtain from 1970
Pay close attention to widely and study application.Wherein, polyaniline, there is itself unique character such as easy preparation process, good
Processability and solubility property, good stability, special physicochemical characteristics, a kind of conduction being most widely used for research is poly-
Close film.Homogeneity, unique oxidation-reduction quality, high conductivity and the strong absorption affinity to electrode surface, polyphenyl due to polyaniline
Amine success is as the good fixing material body plan electrochemica biological of fixing various biomolecule such as enzyme, protein, DNA etc.
Sensor also shows fabulous performance.
The research and development of the preparation method of the organic-inorganic hybrid material being combined into by organic material and inorganic material are in recent years
The study hotspot come.Can realize well organic-inorganic material is worked in coordination with by the component controlling organic-inorganic material
The control of the solid interface character of effect and body plan thereof, which results in the attention of researchers and is widely applied.Utilize organic
Inorganic hybrid material modified electrode body plan electrochemical sensor, it is shown that the advantage of its uniqueness such as three-dimensional rigid structure, to electricity
Stable and the strong adsorption on surface, pole.
In various electrogenerated chemiluminescence systems, luminol ECL system, due to its relatively low oxidizing potential, more cheap
Luminescence reagent and higher luminous efficiency, be the Ru (bpy) that continues3 2+The most widely used ECL system of ECL system.Luminol
Electrogenerated chemiluminescence behavior depend on the apparent condition of applied voltage, electrode material and electrode.Although luminol is at positive potential
And all have electrogenerated chemiluminescence under nagative potential, but major part research is concentrated mainly on luminol institute oxidized on modified electrode
The anodic electrochemiluminescence caused.Reduction reaction between deprotonation luminol and dissolved oxygen and the electrode of oxide layer covering
And the thermoelectron that semi-conducting electrode is launched is the two kinds of main paties producing luminol cathode techniques, but the negative electrode to luminol
The research of electrogenerated chemiluminescence only has several documents.Therefore the various Novel electric of body plan is studied by various chemical modification methods
Cause the interface of chemiluminescence sensor, it is achieved the chemiluminescent sensitivity of luminol cathodic electrochromic and the raising of stability, it will
It it is the research work with practical significance.
Summary of the invention
It is an object of the invention to provide a kind of luminol cathodic electrochromic chemistry based on ordered mesopore carbon and polyaniline to send out
Light excites new method and a kind of electrochemical luminous sensor based on organic-inorganic nanocomposite film.To be had by cyclic voltammetry
It is multiple that machine high molecular polymer-polyaniline is aggregated on DIC nano material-ordered mesopore carbon form organic-inorganic hybrid material
Closing film, and modified glassy carbon electrode surface construction work electrode, phosphate buffer solution, as electrolyte buffer system, can swash
Send out luminol and obtain sensitive, the stable electrogenerated chemiluminescence radiation signal on cathodic electrochromic chemiluminescence passage.
For realizing goal of the invention, the present invention adopts the following technical scheme that
A kind of luminol cathodic electrochromic chemiluminescence based on ordered mesopore carbon and polyaniline of the present invention excites new method,
It is characterized in that, comprise the following steps:
(1) polishing of glass-carbon electrode: glass-carbon electrode first mechanical grinding polishing on the chamois leather be covered with alumina powder, uses secondary
Remained on surface powder is removed in washing, then moves into cleaning in ultrasonic water bath, until cleaning up, the most sequentially with ethanol, and diluted acid and water
Thoroughly washing；
(2) preparation of ordered mesopore carbon/polyaniline composite film modified electrode: the CMK-3 solution taking certain volume drips in clean
Glassy carbon electrode surface also allows solvent naturally volatilize；Dried CMK modified electrode is placed in the sulfuric acid solution containing aniline,
In scanning voltage scope-0.2～1.2V, sweep applying cyclic voltammetric under fast 50 mV/ s and circulate a few, prepared ordered mesopore carbon/
Polyaniline composite film modified electrode；
(3) three-electrode system is used to test, with ordered mesopore carbon/polyaniline composite film modified electrode as working electrode, platinum
Silk electrode is to electrode, and Ag/ AgCl is reference electrode, above-mentioned three electrodes is inserted the phosphate buffer solution containing luminol, executes
Adding cyclic voltammetry scan voltage, working electrode surface produces electrogenerated chemiluminescence radiation, it is thus achieved that the cathodic electrochromic chemistry of luminol
Luminous, gathers, with photodetector, the optical signal that solution produces.
Described CMK-3 solution uses CMK-3 and solvent dimethylformamide configuration to form, and CMK-3 solution concentration is
0.5mg/ml, volume used is 2 μ l.
In the sulfuric acid solution containing aniline, the solubility of aniline solution is 0.1mol/ml, and the solubility of sulfuric acid solution is
0.5mol/ml。
The polymerization number of turns of above-mentioned polyaniline is cyclic voltammetric circulation 10 circle.
Phosphate buffer solution in above-mentioned steps (3), its PH=6.0～9.0.
In above-mentioned steps (3), cyclic voltammetry scan applies voltage range is 0.3V～-1.0V.
In above-mentioned steps (3), the electrogenerated chemiluminescence passage of luminol is for have a cathodic electrochromic chemiluminescence at-0.5V
ECL。
In above-mentioned steps (3), the concentration range of luminol is 1.0 × 10−7-5.0×10−5 mol/L。
A kind of electrochemical luminous sensor based on organic-inorganic nanocomposite film of the present invention, including work electricity
Pole, platinum electrode are for being reference electrode to electrode and Ag/ AgCl, it is characterised in that described working electrode uses order mesoporous
Carbon/polyaniline composite film modified electrode, it is prepared from by the method for following step, 1) polishing of glass-carbon electrode: glass carbon electricity
Pole first mechanical grinding polishing on the chamois leather be covered with alumina powder, removes remained on surface powder with secondary washing, then moves into super
Cleaning in sound water-bath, until cleaning up, the most sequentially with ethanol, diluted acid and water thoroughly wash；2) ordered mesopore carbon/polyaniline
The preparation of complex film modified electrode: the CMK-3 solution taking certain volume drips in clean glassy carbon electrode surface and makes solvent natural
Volatilize；Dried CMK modified electrode is placed in the sulfuric acid solution containing aniline, in scanning voltage scope-0.2～
1.2V, sweeping speed is to apply cyclic voltammetric under 50 mV/ s to circulate a few, prepares ordered mesopore carbon/polyaniline composite film and modifies electricity
Pole.
Above-mentioned CMK-3 solution uses CMK-3 and solvent dimethylformamide configuration to form, and CMK-3 solution concentration is
0.5mg/ml, volume used is 2 μ l；In the sulfuric acid solution containing aniline, the solubility of aniline solution is 0.1mol/ml, and sulphuric acid is molten
The solubility of liquid is 0.5mol/ml；The polymerization number of turns of polyaniline is cyclic voltammetric circulation 10 circle.
Above-mentioned phosphate buffer solution, its PH=6.0～9.0.Cyclic voltammetry scan apply voltage range be 0.3V～-
1.0V。
The electrogenerated chemiluminescence passage of above-mentioned luminol is for have a cathodic electrochromic chemiluminescence ECL at-0.5V.
The concentration range of above-mentioned luminol is 1.0 × 10−7-5.0×10−5 mol/L。
Advantages of the present invention is:
(1) present invention realizes the cooperative effect to organic-inorganic material well by the component controlling organic-inorganic material, profit
The advantage such as three-dimensional rigid structure, electrode surface of its uniqueness is shown with the electrochemical sensor of organic-inorganic hybrid material body plan
Stability etc.；
(2) present invention excites luminol to obtain in cathodic electrochromic chemiluminescence by means of organic-inorganic hybrid material modified electrode
Sensitive, stable electrogenerated chemiluminescence radiation signal on passage, will be enlarged by its application prospect in analytical chemistry field；
(3) preparation process of the present invention is simple, and the Electrochemiluminescsensor sensor of preparation has good electrochemiluminescence performance, pole
Good bio-compatibility, has certain application prospect at novel Electrochemiluminescsensor sensor and biomedical sector.
Accompanying drawing explanation
Fig. 1 is the preparation process schematic diagram of CMK/PAN composite membrane electrochemical luminous sensor of the present invention.
Fig. 2 A is the TEM phenogram of CMK-3.
Fig. 2 B is the SEM phenogram of the complex film modified glass-carbon electrode of CMK/PAN.
Fig. 3 is in pH 7.5 phosphate buffer solution, naked GCE(a), CMK/GCE(b), PAN/GCE (c), CMK/PAN/GCE
D () is containing 2 × 10-5ECL behavior figure in PBS 7.5 solution of mol/L luminol.
Fig. 4 is in pH 7.5 phosphate buffer solution, the luminol linear sound on naked GCE, PAN/GCE, CMK/PAN/GCE
Answering areal map, a, b, the c in figure is luminol linear response range on naked GCE, PAN/GCE, CMK/PAN/GCE respectively
Figure.
Fig. 5 is in pH 7.5 phosphate buffer solution, linear on the complex film modified glass-carbon electrode of CMK/PAN of hydrogen peroxide
Response range figure.
Detailed description of the invention
Present invention the following example further illustrates the present invention, but protection scope of the present invention is not limited to following reality
Execute example.
CMK-3 in following embodiment is commercially available prod, and Nanjing Xian Feng Nono-material Science & Technology Ltd. can be used to supply
The product answered.
Embodiment 1
(1) take 1.0mgCMK-3 and be scattered in 2ml dimethylformamide DMF solution preparation 0.5mg/ml CMK-3 solution.Fig. 2 A
Give viewed pattern and knot under ordered mesopore carbon CMK-3 transmission on the scene electron scanning Electronic Speculum instrument (FE TEM)
Structure, we can see that the orderly hexagonal array that CMK-3 is made up of carbon nano rod, it is shown that in good order from Fig. 2 A
Loose structure.
(2) glass-carbon electrode first mechanical grinding polishing on the chamois leather be covered with alumina powder, goes to surface with secondary washing
Residual powder, then move into cleaning in ultrasonic water bath, each 2 minutes, in triplicate, until cleaning up, finally with ethanol, diluted acid
Thoroughly wash with water；Take 2 μ l 0.5mg/ml CMK-3 solution drip in clean glassy carbon electrode surface and allow solvent naturally volatilize shape
Become the CMK modified electrode being dried；Dried CMK modified electrode is placed on the 0.5 mol/L sulfur containing 0.1 mol/L aniline
In acid solution, in scanning voltage scope-0.2～1.2V, sweeping speed is to apply cyclic voltammetric circulation 10 circle under 50 mV/ s, prepares and has
The complex film modified electrode of CMK/PAN.Fig. 2 B shows that the complex film modified glass-carbon electrode of CMK/PAN is in Flied emission electron scanning Electronic Speculum
Surface topography under instrument (FE SEM), as can be seen from Figure 2B by electropolymerization method, polyaniline has been evenly distributed in Jie
The electrode surface that hole carbon is modified.
Embodiment 2
(1) polishing of glass-carbon electrode and the preparation of naked glass-carbon electrode: glass-carbon electrode is first on the chamois leather being covered with alumina powder
Mechanical grinding polishes, and removes remained on surface powder with secondary washing, then moves into cleaning in ultrasonic water bath, each 2 minutes, repeats three
Secondary, until cleaning up, finally with ethanol, diluted acid and water thoroughly wash；
(2) preparation of ordered mesopore carbon (CMK) film modified electrode: take the CMK-3 solution (being dissolved in DMF) of 2 μ l 0.5mg/ml,
Drip in clean naked glassy carbon electrode surface and allow solvent naturally volatilize；
(3) preparation of polyaniline (PAN) film modified electrode: clean naked glass-carbon electrode is placed on containing 0.1 mol/L aniline
0.5 M H2SO4In sulfuric acid solution, using cyclic voltammetry, at scanning voltage scope-0.2V～1.2V, sweeping speed is 50 mV/ s
Lower circulation 10 is enclosed；
(4) preparation of the complex film modified electrode of CMK/PAN: take 2 μ l 0.5mg/ml CMK-3 solution (being dissolved in DMF), drip in
Clean naked glassy carbon electrode surface also allows solvent naturally volatilize, and is placed on dried CMK modified electrode containing 0.1 mol/L
0.5 M H of aniline2SO4In sulfuric acid solution, using cyclic voltammetry, at scanning voltage scope-0.2V～1.2V, sweeping speed is 50
10 circles are circulated under mV/ s；
(5) using three-electrode system to test, with naked glass-carbon electrode as working electrode, platinum electrode is to electrode, Ag/
AgCl is reference electrode, inserts above-mentioned three electrodes containing 2.0 × 10−5Mol/L luminol pH 7.5 phosphate buffer solution, executes
Adding cyclic voltammetry scan voltage, working electrode surface produces electrogenerated chemiluminescence radiation, obtains naked GCE at the pH containing luminol
ECL behavior (as shown in a in Fig. 3) in 7.5 phosphate buffer solutions；
(6) using three-electrode system to test, with CMK film modified electrode as working electrode, platinum electrode is to electrode, Ag/
AgCl is reference electrode, inserts above-mentioned three electrodes containing 2.0 × 10−5Mol/L luminol pH 7.5 phosphate buffer solution, executes
Adding cyclic voltammetry scan voltage, working electrode surface produces electrogenerated chemiluminescence radiation, obtains CMK film modified electrode containing Shandong
The ECL behavior (as shown in the b in Fig. 3) of pH 7.5 phosphate buffer solution of minot, luminol is on the film modified GCE of mesoporous carbon
ECL intensity be almost its on naked glass-carbon electrode more than 3 times, this is mainly due to the introducing of the mesoporous carbon with bigger serface
The surface texture improving electrode greatly makes electrode surface be porous, and beneficially reactant is in the mass transfer mistake of electrode surface
Journey；
(7) using three-electrode system to test, with PAN film modified electrode as working electrode, platinum electrode is to electrode, Ag/
AgCl is reference electrode, inserts above-mentioned three electrodes containing 2.0 × 10−5Mol/L luminol pH 7.5 phosphate buffer solution, executes
Adding cyclic voltammetry scan voltage, working electrode surface produces electrogenerated chemiluminescence radiation, obtains PAN film modified electrode containing Shandong
ECL behavior (as shown in the c in Fig. 3) in pH 7.5 phosphate buffer solution of minot, luminol is modified on GCE in polymeric membrane
ECL intensity be almost its on naked glass-carbon electrode more than 4 times, this is mainly due to the drawing of polyaniline with excellent conductive performance
Entering to improve greatly the conductivity of electrode, the reduction to dissolved oxygen has certain catalytic action；
(8) using three-electrode system to test, with the complex film modified electrode of CMK/PAN as working electrode, platinum electrode is right
Electrode, Ag/ AgCl is reference electrode, inserts above-mentioned three electrodes containing 2.0 × 10−5Mol/L luminol pH 7.5 phosphoric acid delays
Dissolved liquid, applies cyclic voltammetry scan voltage, and working electrode surface produces electrogenerated chemiluminescence radiation, and CMK/PAN composite membrane is repaiied
Decorations electrode ECL behavior (as shown in the d in Fig. 3) in pH 7.5 phosphate buffer solution containing luminol, due to polyaniline
And the synergism after mesoporous carbon hydridization, the negative electrode ECL intensity of luminol further enhances.
Embodiment 3
(1) polishing of glass-carbon electrode and the preparation of naked glass-carbon electrode: glass-carbon electrode is first on the chamois leather being covered with alumina powder
Mechanical grinding polishes, and removes remained on surface powder with secondary washing, then moves into cleaning in ultrasonic water bath, each 2 minutes, repeats three
Secondary, until cleaning up, finally with ethanol, diluted acid and water thoroughly wash；
(2) preparation of polyaniline (PAN) film modified electrode: clean naked glass-carbon electrode is placed on containing 0.1 mol/L aniline
0.5 mol/L H2SO4In sulfuric acid solution, using cyclic voltammetry, at scanning voltage scope-0.2V～1.2V, sweeping speed is 50
10 circles are circulated under mV/ s；
(3) preparation of the complex film modified electrode of CMK/PAN: take 2 μ l 0.5mg/ml CMK-3 solution (being dissolved in DMF), drip in
Clean glassy carbon electrode surface also allows solvent naturally volatilize, and is placed on dried CMK modified electrode containing 0.1 mol/L benzene
0.5 mol/L H of amine2SO4In sulfuric acid solution, using cyclic voltammetry, at scanning voltage scope-0.2V～1.2V, sweeping speed is
10 circles are circulated under 50 mV/ s；
(4) using three-electrode system to test, with naked glass-carbon electrode as working electrode, platinum electrode is to electrode, Ag/
AgCl is reference electrode, and by above-mentioned three electrodes insertions, containing variable concentrations, (concentration range is 5.0 × 10−6-5.0×10−5 mol/
L) luminol pH 7.5 phosphate buffer solution, applies cyclic voltammetry scan voltage, and working electrode surface produces electroluminescent chemistry and sends out
Light radiation, obtains luminol naked GCE linear response range (as shown in a in Fig. 4)；
(5) using three-electrode system to test, with PAN film modified electrode as working electrode, platinum electrode is to electrode, Ag/
AgCl is reference electrode, and by above-mentioned three electrodes insertions, containing variable concentrations, (concentration range is 1.0 × 10−6-5.0×10−5 mol/
L) luminol pH 7.5 phosphate buffer solution, applies cyclic voltammetry scan voltage, and working electrode surface produces electroluminescent chemistry and sends out
Light radiation, obtains luminol linear response range (as shown in the b in Fig. 4) on the film modified glass-carbon electrode of PAN；
(6) using three-electrode system to test, with the complex film modified electrode of CMK/PAN as working electrode, platinum electrode is right
Electrode, Ag/ AgCl is reference electrode, and by above-mentioned three electrodes insertions, containing variable concentrations, (concentration range is 1.0 × 10−7-5.0×
10−5Mol/L) luminol pH 7.5 phosphate buffer solution, applies cyclic voltammetry scan voltage, and working electrode surface produces electricity
Cause chemiluminescence radiation, obtain luminol linear response range on the complex film modified glass-carbon electrode of CMK/PAN (in Fig. 4
C shown in), the complex film modified GCE of CMK/PAN shows the strongest ECL intensity and the widest linear response range to luminol,
Indicate and revealed by the ECL sensor sheet of the organic-inorganic hybrid material modified membrane institute body plan of polyaniline and mesoporous carbon hydridization
Higher performance.
Embodiment 4
(1) polishing of glass-carbon electrode: glass-carbon electrode first mechanical grinding polishing on the chamois leather be covered with alumina powder, uses secondary
Remained on surface powder is removed in washing, then moves into cleaning in ultrasonic water bath, each 2-3 minute, in triplicate, until cleaning up,
Afterwards with ethanol, diluted acid and water thoroughly wash；
(2) preparation of the complex film modified electrode of CMK/PAN: take 2 μ l 0.5mg/mlCMK-3 solution (being dissolved in DMF), drips in dry
Clean glassy carbon electrode surface also allows solvent naturally volatilize, and is placed on dried CMK modified electrode containing 0.1 mol/L aniline
0.5 mol/L H2SO4In sulfuric acid solution, using cyclic voltammetry, at scanning voltage scope-0.2V～1.2V, sweeping speed is 50
10 circles are circulated under mV/ s.
(3) three-electrode system is used to test, with the complex film modified electrode of CMK/PAN as working electrode, platinum electrode
For to electrode, Ag/ AgCl is reference electrode, inserts above-mentioned three electrodes containing 2 × 10-5 Mol/L luminol and variable concentrations
(concentration range is 1.0 × 10−9-5.0×10−5In pH 7.5 phosphate buffer solution of hydrogen peroxide mol/L), based on Rumi
The electrogenerated chemiluminescence passage of promise, applies cyclic voltammetry scan voltage, gathers, with photodetector, the optical signal that solution produces.In Shandong
The high concentration 1.0 × 10 of minot−7～1.0 × 10−5 In the range of mol/L, the concentration of hydrogen peroxide becomes with the ECL intensity of luminol
Linear relationship, its linear correlation equation is I=1 × 1010C+1864(R2=0.999)；And luminol low concentration 1.0 ×
10−9～1.0 × 10−7In the range of mol/L, the logarithm of the concentration of hydrogen peroxide is linear with the logarithm of the ECL intensity of luminol
Relation, its linear correlation equation is log (I)=0.21log (C)+4.634(R2=0.998), wherein I is the ECL of luminol
Intensity, C is the concentration of hydrogen peroxide.
Claims (10)
1. luminol cathodic electrochromic chemiluminescence based on ordered mesopore carbon and polyaniline excites a new method, and its feature exists
In, comprise the following steps:
The polishing of glass-carbon electrode: glass-carbon electrode first mechanical grinding polishing on the chamois leather be covered with alumina powder, uses secondary water
Washing away remained on surface powder, then move into cleaning in ultrasonic water bath, until cleaning up, the most sequentially with ethanol, diluted acid and water are thorough
The end, washs；
The preparation of ordered mesopore carbon/polyaniline composite film modified electrode: the CMK-3 solution taking certain volume drips in clean glass
Carbon electrodes also allows solvent naturally volatilize；Dried CMK modified electrode is placed in the sulfuric acid solution containing aniline,
Scanning voltage scope-0.2～1.2V, sweeps applying cyclic voltammetric under fast 50 mV/ s and circulates a few, prepared ordered mesopore carbon/poly-
The complex film modified electrode of aniline；
Three-electrode system is used to test, with ordered mesopore carbon/polyaniline composite film modified electrode as working electrode, platinum filament electricity
Extremely to electrode, Ag/ AgCl is reference electrode, above-mentioned three electrodes is inserted the phosphate buffer solution containing luminol, applies to follow
Ring voltammetric scan voltage, working electrode surface produces electrogenerated chemiluminescence radiation, it is thus achieved that the cathodic electrochromic chemiluminescence of luminol
Passage, gathers, with photodetector, the optical signal that solution produces.
Method the most according to claim 1, it is characterised in that described CMK-3 solution is to use CMK-3 and dimethyl formyl
Amine solvent configuration, CMK-3 solution concentration is 0.5mg/ml, and volume used is 2 μ l.
Method the most according to claim 1 and 2, it is characterised in that aniline solution in the sulfuric acid solution containing aniline
Solubility is 0.1mol/ml, and the solubility of sulfuric acid solution is 0.5mol/ml.
Method the most according to claim 3, it is characterised in that the polymerization number of turns of polyaniline is cyclic voltammetric circulation 10 circle.
Method the most according to claim 3, it is characterised in that phosphate buffer solution in step (3), its PH=6.0～9.0.
Method the most according to claim 3, it is characterised in that in step (3), cyclic voltammetry scan applying voltage range is
0.3V～-1.0V.
Method the most according to claim 3, it is characterised in that in step (3), the electrogenerated chemiluminescence passage of luminol is
A cathodic electrochromic chemiluminescence ECL is had at-0.5V.
Method the most according to claim 3, it is characterised in that in step (3), the concentration range of luminol is 1.0 × 10−7-
5.0×10−5 mol/L。
9. an electrochemical luminous sensor based on organic-inorganic nanocomposite film, is right including working electrode, platinum electrode
Electrode and Ag/ AgCl are reference electrode, it is characterised in that described working electrode uses ordered mesopore carbon/polyaniline composite film
Modified electrode, it is prepared from by the method for following step, 1) polishing of glass-carbon electrode: first glass-carbon electrode is being covered with oxidation
Mechanical grinding polishing on the chamois leather of aluminium powder, removes remained on surface powder with secondary washing, then moves into cleaning in ultrasonic water bath, until
Cleaning up, the most sequentially with ethanol, diluted acid and water thoroughly wash；2) ordered mesopore carbon/polyaniline composite film modified electrode
Preparation: the CMK-3 solution taking certain volume drips in clean glassy carbon electrode surface and allows solvent naturally volatilize；By dried
CMK modified electrode is placed in the sulfuric acid solution containing aniline, and in scanning voltage scope-0.2～1.2V, sweeping speed is 50 mV/
Apply cyclic voltammetric under s and circulate a few, prepare ordered mesopore carbon/polyaniline composite film modified electrode.
Electrochemical luminous sensor the most according to claim 9, it is characterised in that described CMK-3 solution is to use CMK-
3 and solvent dimethylformamide configuration, CMK-3 solution concentration is 0.5mg/ml, and volume used is 2 μ l；Containing benzene
In the sulfuric acid solution of amine, the solubility of aniline solution is 0.1mol/ml, and the solubility of sulfuric acid solution is 0.5mol/ml；Gathering of polyaniline
Closing the number of turns is cyclic voltammetric circulation 10 circle.
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| CN110323464A (en) * | 2019-06-27 | 2019-10-11 | 渤海大学 | A kind of polyaniline-carbon nanotube-tin oxide-polyacrylonitrile composite diaphragm potassium air cell |
| CN115236156A (en) * | 2022-07-18 | 2022-10-25 | 常州大学 | PAN-BSA (PAN-bovine serum albumin) compound modified electrode for chiral recognition of tryptophan enantiomer as well as preparation method and application of PAN-BSA compound modified electrode |
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|---|---|---|---|---|
| CN110323464A (en) * | 2019-06-27 | 2019-10-11 | 渤海大学 | A kind of polyaniline-carbon nanotube-tin oxide-polyacrylonitrile composite diaphragm potassium air cell |
| CN110247060A (en) * | 2019-06-30 | 2019-09-17 | 哈尔滨工业大学 | PANI/Go/PAN nanofiber membrane composite potassium cathode of air battery and preparation method thereof |
| CN115236156A (en) * | 2022-07-18 | 2022-10-25 | 常州大学 | PAN-BSA (PAN-bovine serum albumin) compound modified electrode for chiral recognition of tryptophan enantiomer as well as preparation method and application of PAN-BSA compound modified electrode |
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