A kind of silicon nano hole road thin film/indium-tin oxide electrode Electrochemical Detection lead ion in order
Method
Technical field
The present invention relates to field of new, be specifically related to a kind of silicon nano hole road thin film in order/indium-tin oxide electrode electrification
The method learning detection lead ion.
Background technology
Lead has that fusing point is low, corrosion-resistant, density is high, is prone to the features such as processing and is widely used in every field.Full generation
Boundary's annual lead consumption is about 4,000,000 tons, but only the lead of 1/4 is recycled, and remaining can give up in different forms such as waste water
The forms such as slag enter in environment thus pollute soil and water body.
In life, human body may take in the lead of trace by the way of diet, such as edible leaded preserved egg, drinks lead content
The water exceeded standard.The lead taken in, after absorption of human body, can be enriched with in human body.Lead is primarily present in skeleton, be enriched on a small quantity liver,
In brain, kidney and blood, being enriched in the amount that internal lead is enriched with according to it, the position of enrichment and human body self are for the sensitivity of lead
And show various harm.Hemopoietic system can be impacted by lead, causes anemia and haemolysis.Take in lead for a long time, can cause chronic
Lead poisoning.Nervous system can be caused serious destruction by the absorption of excess lead, the diseases such as headache, hypomnesis or even hallucination occurs
Shape.Child is to the sensitivity of lead compared to adult Geng Gao, and children's lead poisoning mainly shows as poor growth, mental retardation, god
Through atrophy etc..Lead poisoning can also result in cancer.In national regulation blood, lead content is lead poisoning more than 100 micrograms per litre, therefore
A kind of method needing to invent simple and effective detection trace lead ion.
The assay method of blood lead content is varied, conventional have atomic absorption spectrography (AAS), Atomic Emission Spectral Analysis method,
Isotope dilution mass spectrometry, potentiometric stripping.But these methods all have some limitations, as atomic absorption spectrography (AAS) by
Relatively low in atomic pola-rizability, the lead for low concentration detects more difficulty.Isotope dilution mass spectrometry detection is sensitive and reliable,
But the method is loaded down with trivial details and time-consuming, and test the expensive equipment of needs, be worth little the most in actual applications.Current potential is molten
Going out method detection sensitive, capacity of resisting disturbance is strong, is more common blood lead analysis method, but need nonetheless remain for blood lead instrument and could measure.
For the detection of complex sample, in said method, sample is required for just can detecting through complicated process.
The patent documentation of publication No. CN 101017149A discloses a kind of disposable blood lead biosensor, profit
Having made working electrode with screen printing technique, to electrode and reference electrode, working electrode, under high voltage aoxidizes, forms carbon oxygen
Functional group, can improve lead ion and be deposited on the ability of electrode surface, thus promote the detection signal of lead ion.The method overcomes
Electrochemical Detection blood lead needs the instrument of specialty, but during the method measures blood lead, the preoxidation process of electrode is relatively
Only can use once for loaded down with trivial details and sensor, therefore bigger obstruction be caused for popularization and application.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of silicon nano hole road thin film in order/indium-tin oxide electrode electricity
The method of chemical detection lead ion, utilizes the orderly silicon nano hole road thin film/indium-tin oxide electrode strong enrichment to lead ion
With the nano pore exclusion effect to most of interfering materials, it is achieved lead ion fast and effeciently electrochemical quantitative is measured.
The method of a kind of orderly silicon nano hole road thin film/indium-tin oxide electrode Electrochemical Detection lead ion, including following step
Rapid:
(1) measuring samples and buffer are mixed to get the liquid to be measured that pH value is 3.6~6.0;
(2) three-electrode system is used, using orderly silicon nano hole road thin film/indium-tin oxide electrode as working electrode, platinum filament
Or platinized platinum is to electrode, silver/silver chloride electrode is reference electrode, and constant voltage method is enriched with the lead ion in liquid to be measured, is enriched with voltage
For-0.8V~-0.6V;
(3) electrode completing enrichment is placed in the buffer that pH value is 3.6~6.0 of blank, utilizes differentiated pulse to lie prostrate
Peace method records peak point current, calculates the plumbum ion concentration in measuring samples according to standard curve;
Described Differential Pulse Voltammetry scanning take-off potential be-0.95V~-0.65V, termination current potential be-0.4V~
0.5V。
The preparation method of orderly silicon nano hole road thin film/tin indium oxide (VOMs/ITO) electrode of the present invention: with Indium sesquioxide.
Stannum (ITO) transparent conducting glass is as substrate, with cetyl trimethylammonium bromide (CTAB) as template, tetraethyl orthosilicate
(TEOS) being silicon source, react in ethanol, water mixed solution, synthesis has obtained the orderly silicon nanometer with cylindrical micelle structure
Duct thin film/indium-tin oxide electrode (CSMs/VOMs/ITO).The CSMs/VOMs/ITO electrode obtained is in ethanol solution hydrochloride
The most removable CTAB of immersion, prepares orderly silicon nano hole road thin film/indium-tin oxide electrode (VOMs/ITO).
The VOMs/ITO electrode of the present invention has three-decker, the most orderly silicon nano hole road thin film, oxygen
Changing indium stannum, glass, wherein orderly silicon nano hole road thin film (VOMs) thickness 80~100nm, pore passage structure is homogeneous, aperture be 2~
3nm, porosity height, and heat stability and chemical stability are high, are a kind of effective nano pore thin film, can be efficiently applied to
The fields such as analysis, sensor.
Owing to the silicone hydroxyl in orderly silicon nano hole road thin film (VOMs) has in the buffer solution that pH value is 3.6~6.0
There is relatively negative Zeta potential, can effectively enriched lead ion, the Electrochemical Detection sensitivity of raising lead ion.Silicon nano hole in order
The Zeta potential that road thin film is born is to be caused by its structure.The structure of silicon nano hole road thin film is sol-gel process gained in order
Silica gel, its pKa value is about 1.7.Therefore, in pH value range used, make material have negative electricity due to the ionization of Si-OH
Position.
If pH value is higher than 6.0, lead ion is susceptible to hydrolysis, affects final detection result.
The buffer system that the present invention selects first has to ensure that lead ion is free and is distributed in solution, as preferably, described slow
Rush liquid be concentration be the Acetic acid-sodium acetate buffer of 0.02mol/L~0.5mol/L, pH value is 3.6~5.6.Due to buffer body
The pH of system can change the binding ability of silicone hydroxyl and lead ion, and the present invention, according to the DPV peak current signal intensity of lead ion, draws
The optimal conditions of pH, more preferably, the pH value of described buffer is 5.6.Under the buffer condition that pH value is 5.6, the present invention's
Detection is limited to 0.087nM, and detection range is 100pmol/L-1 μm ol/L.
In order to ensure pH value and the buffer capacity of liquid to be measured, measuring samples is 1:1~1 with the mixed proportion of buffer:
100.As preferably, mixed proportion is 1:40.
The present invention uses three-electrode system, and orderly silicon nano hole road thin film/indium-tin oxide electrode is as working electrode, platinum electricity
Pole is as to electrode, and Ag/AgCl electrode is as reference electrode.
Enrichment voltage is it is generally required to be higher than the oxidation-reduction potential of lead ion so that ion can deposit at electrode surface.
Enrichment voltage is-0.8V~-0.6V, and under the conditions of this constant voltage, the present invention realizes the enrichment just for lead ion.If voltage is low
In-0.8V, ITO layer can be reduced;Voltage can cause lead ion to be enriched with higher than-0.6V, follow-up lead ion cannot be detected.
Further preferably, enrichment voltage is-0.75V.
As preferably, constant voltage enrichment time is 20s~600s.Enrichment time is short, and lead ion enriching quantity is inadequate, differential arteries and veins
The electrochemical signals rushing voltammetry is weak, it is impossible to accurately detect the lead ion content of testing sample;Enrichment time is long, can make detection
Time is tediously long, and causes the change of electrode surface form.More preferably, enrichment time is 420s.
In enrichment process, liquid to be measured is carried out continuously stirred.As preferably, described stirring is magnetic agitation.
The present invention uses Differential Pulse Voltammetry (DPV) can obtain lead ion Stripping Currents signal.Take-off potential is main
Be the maximum potential can born according to ITO electrode self and lead ion dissolution current potential formulate, ITO electrode less than-
Under the current potential of 1.0V, redox reaction can occur self, and make electrode be destroyed, therefore our take-off potential minimum can not
Less than-1.0V, the DPV spike potential of lead ion dissolution is-0.55V, and therefore take-off potential have to be lower than-0.55V.Terminate current potential
Selection is that the width according to peak determines, terminates current potential and has only to produce completely so that the peak shape of lead ion.The most excellent
Choosing, the take-off potential of Differential Pulse Voltammetry scanning is-0.75V, and terminating current potential is-0.2V.
When plumbum ion concentration is 100pmol/L-1 μm ol/L, DPV peak current has linearly with the logarithm of plumbum ion concentration
Relation, can realize the detection by quantitative to lead ion.
In step (3), the method for building up of described standard curve is:
A () prepares the standard substance that pH value is 3.6~6.0 of the logarithm value distribution gradient of one group of plumbum ion concentration;
B () uses three-electrode system, using orderly silicon nano hole road thin film/indium-tin oxide electrode as working electrode, platinum filament
Or platinized platinum is to electrode, silver/silver chloride electrode is reference electrode, and constant voltage method is enriched with the lead ion in each standard substance, enrichment electricity
Pressure is-0.8V~-0.6V;
C the electrode completing enrichment is placed in the buffer that pH value is 3.6~6.0 of blank by (), utilize differentiated pulse to lie prostrate
Peace method records the peak point current of each standard substance, and the take-off potential of described Differential Pulse Voltammetry scanning is-0.95V~-0.65V,
Terminating current potential is-0.4V~0.5V;
D () draws standard curve according to the logarithm value of plumbum ion concentration with peak point current.
The electrochemistry experiment condition of Criterion curve keeps consistent with the condition of detection measuring samples.As preferably, institute
The buffer system stating standard substance is Acetic acid-sodium acetate buffer.
Described measuring samples is blood serum sample, water sample, foodstuff samples or the pure lead ion sample separated.
Research shows, the detection method of the present invention can optionally detect the lead ion in measuring samples.When to be checked
Containing macromolecular substances such as ascorbic acid, glucose, bovine serum albumin, catalase, thrombin, dopamine in sample
Time, do not affect the detection to lead ion.This is mainly due to the volume exclusion in orderly silicon nano hole road.Owing to orderly silicon is received
The duct of metre hole road thin film is only 2~3nm, and macromolecular substances cannot arrive electrode surface generation current signal by passing hole channel, from
And avoid the mensuration of lead ion content is interfered.Therefore, the inventive method is applicable to the blood serum sample that detection separates.
The beneficial effect that the present invention possesses:
(1) the VOMs/ITO electrode of the present invention has abundant silicone hydroxyl, under the conditions of acidic buffer effective enriched lead from
Son, when pH value is 5.6, the detection of the inventive method is limited to 0.087nM, and the lead ion detection for trace has the highest
Sensitivity.
(2) being to determine with the oxidation-reduction potential of every kind of ion self due to the spike potential of DPV, therefore every kind of ion is only
Can there is a DPV spike potential, the enrichment voltage of the present invention and DPV voltage are all determined with the oxidation-reduction potential of lead ion self
Fixed, therefore, the detection of other ion pairs present invention does not produce interference.
(3) the VOMs/ITO electrode of the present invention effectively can enter duct by exclusion biomacromolecule, it is adaptable to serum etc
Lead ion detection in complex sample.
(4) the inventive method without carrying out the pretreatment such as oxidation operation to actual sample, easy and simple to handle;Electrode can be repeatedly
Use, cost-effective.
(5) present invention detects speed soon, and detection efficiency is high.
Accompanying drawing explanation
Fig. 1 is CSMs/VOMs/ITO electrode (a) and VOMs/ITO electrode (b) is in methanol ferrocene (solid line) and ferrum cyaniding
Cyclic voltammetry curve in potassium (dotted line) solution.
Fig. 2 be the Zeta potential of three kinds of electrodes be ITO electrode with pH value variation diagram, triangular coordinate point, circular coordinate points
For CSMs/VOMs/ITO electrode, square coordinate points is VOMs/ITO electrode.
Fig. 3 is the scanning electron microscope diagram of VOMs/ITO electrode sections.
Fig. 4 is the high resolution transmission electron microscopy figure of CSMs/VOMs/ITO electrode (a) and VOMs/ITO electrode (b).
Fig. 5 is to be enriched with through constant voltage in the different pH value Acetic acid-sodium acetate buffer containing 1 μm ol/L lead ion
After, DPV method records peak current intensity.
When Fig. 6 is that constant voltage enrichment is different in the Acetic acid-sodium acetate buffer (pH 5.6) containing 1 μm ol/L lead ion
After between, DPV method records peak current intensity.
Fig. 7 is the recycling property of VOMs/ITO electrode.
Fig. 8 is the anti-interference of VOMs/ITO electrode.
Fig. 9 is the DPV curve of VOMs/ITO electrode detection variable concentrations lead ion.
Figure 10 is the linearity curve of plumbum ion concentration logarithm and peak current intensity.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
1, the preparation of VOMs/ITO electrode
(1) precursor solution preparation: weigh 0.16g CTAB, adds 70ml deionized water and is sufficiently stirred for, be sequentially added into
30ml ethanol, 12 μ L ammonia (20-25%), 80 μ L TEOS, stir 10min.
(2) prepared by CSMs/VOMs/ITO electrode: poured in reactor by precursor solution, and puts into clean ITO electricity
Pole.Being sealed by reactor, heat 24h in 60 DEG C of water-baths, after having reacted, sample is clean with a large amount of deionized water wash, nitrogen
Drying up, sample is placed in aging 12h in 100 DEG C of baking ovens.
(3) prepared by VOMs/ITO electrode: CSMs/VOMs/ITO electrode is placed in the hydrochloric acid/ethanol solution of 0.1mol/L, stirs
Mix the CTAB micelle in the removable electrode of 10min, obtain VOMs/ITO electrode.
2, characterize
VOMs/ITO electrode in embodiment 1 is carried out electrochemical probe sign, Zeta potential, scanning electron microscope, thoroughly
Penetrating the tests such as ultramicroscope to characterize, the Measurement results obtained is as shown in Fig. 1~8.
Neutral molecule methanol ferrocene shown in Fig. 1 a can produce current signal in CSMs/VOMs/ITO electrode duct,
And anion fewrricyanic acid root can not produce current signal in CSMs/VOMs/ITO electrode duct, these result valid certificates
The electric charge exclusion effect of CTAB micelle in CSMs/VOMs/ITO electrode, hinders anion and enters duct arrival electrode surface, because of
This curve obtained only shows capacitance current.Methanol ferrocene and the potassium ferricyanide shown in Fig. 1 b all can be in VOMs/ITO electrode ducts
Producing current signal, in electrode is described, CTAB micelle has been removed.
Shown in Fig. 2 under conditions of pH=5.6 the Zeta potential of VOMs/ITO electrode compared to CSMs/VOMs/ITO electrode
More negative with ITO electrode, this result valid certificates VOMs/ITO electrode has stronger enrichment for lead ion, and this phenomenon is
Electronegative ITO surface and the synergistic result of silicone hydroxyl.
There are obvious three-decker, the most orderly silicon nano hole in the cross section of VOMs/ITO electrode shown in Fig. 3
Road thin film, tin indium oxide, glass.Wherein silicon nano hole road thin film layer thickness is 85.7nm in order, has ultra-thin construction features.
Fig. 4 is the high resolution transmission electron microscope figure of CSMs/VOMs/ITO electrode (a) and VOMs/ITO electrode (b),
It can be seen that CSMs/VOMs/ITO electrode (a) pore passage structure is homogeneous, aperture is 2~3nm and porosity is high, removes CTAB micelle
After, VOMs/ITO electrode (b) still possesses these features, illustrates that the removal of CTAB does not interferes with the pore passage structure of thin film.
Fig. 5 is that the condition that VOMs/ITO electrode detects for lead ion is preferred.1 μ wherein obtained under conditions of pH 5.6
The peak current signal of mol/L lead ion is the strongest, and the Acetic acid-sodium acetate buffer that subsequent experimental selects pH to be 5.6 is electrolyte.
Fig. 6 is that the condition that VOMs/ITO electrode detects for lead ion is preferred.The peak current signal of 1 μm ol/L lead ion with
The increase of enrichment time and increase, after the time reaches 420s, VOMs/ITO electrode basically reaches full for the enrichment of lead ion
With, it is considered to the factors such as conventional efficient, therefore subsequent experimental selects the time that 420s is enriched with as constant voltage method.
Fig. 7 is the recycling property of VOMs/ITO electrode.Same concentration lead ion is detected by electrode repeatedly, passes through
10 times circulation rear electrode still keeps 90% to lead ion response.The result shows, electrode has and prominent recycles performance.
Fig. 8 is the anti-interference of VOMs/ITO electrode.By the lead ion of 0.2 μ g/ml respectively with the Vitamin C of 60 μ g/ml
Acid, glucose, bovine serum albumin, catalase, thrombin, dopamine mixes, and measures plumbum ion concentration, has all obtained very
The good response rate.The result shows, ascorbic acid, glucose, bovine serum albumin, catalase, thrombin, dopamine
The equimolecular mensuration to lead ion, does not the most affect.
3, working curve is set up
(1) preparation titer: in the NaAc_HAc buffer solution of pH 5.6, a series of plumbum ion concentrations are respectively
0.1、0.5、1、5、10、50、100、400、500、800、1000nmol/L。
(2) VOMs/ITO electrode step 1 prepared is as working electrode, and platinum electrode is reference electrode, and Ag/AgCl is ginseng
Ratio electrode, is separately added into the lead ion solution of a series of concentration known wherein, and under-0.75V voltage, constant voltage is enriched with
420s。
(3) Differential Pulse Voltammetry (DPV) is utilized to measure after being washed with deionized water only by the electrode completing enrichment different dense
The peak current intensity of degree lead ion, the wherein running parameter of Differential Pulse Voltammetry: take-off potential is-0.75V, terminate current potential
For-0.2V.
(4) drawing curve: with peak current intensity as vertical coordinate, with the logarithm of plumbum ion concentration as abscissa, draws
Working curve.
Fig. 9 is the VOMs/ITO electrode DPV curve for variable concentrations lead ion, and Figure 10 is logarithm and the peak current of concentration
The linearity curve of intensity, in figure, linear relationship is good, the result shows that VOMs/ITO electrode detects for the lead ion of trace
There is the highest sensitivity, detection limit and detection range.Detection is limited to 0.087nM, and detection range is 100pmol/L-1 μ
mol/L。
4, the Electrochemical Detection of unknown sample
Measure the DPV peak current intensity of unknown concentration actual sample in aforementioned manners, calculate lead according to working curve
Ion concentration.
Embodiment 2
By artificial lake water with pH 5.6 Acetic acid-sodium acetate buffer with the dilution proportion of 1:1, use standard addition method to divide
Do not add 1nmol/L, 10nmol/L and 500nmol/L lead ion solution.
VOMs/ITO electrode step 1 in embodiment 1 prepared is as working electrode, and platinum electrode is reference electrode, Ag/
AgCl is reference electrode, is separately added into above-mentioned solution wherein, under-0.75V voltage, and constant voltage enrichment 420s.Then by complete
The electrode becoming enrichment utilizes Differential Pulse Voltammetry (DPV) to measure the peak current of variable concentrations lead ion after being washed with deionized water only
Intensity, the wherein running parameter of Differential Pulse Voltammetry: take-off potential is-0.75V, terminating current potential is-0.2V.
The working curve set up according to step 3 in embodiment 1 calculates plumbum ion concentration, and then calculates the response rate, and result is shown in
Table 1.
Embodiment 3
By the human serum of separation with pH 5.6 Acetic acid-sodium acetate buffer with the dilution proportion of 1:40, use Standard entertion
Method is separately added into 1nmol/L, 10nmol/L and 500nmol/L lead ion solution.
VOMs/ITO electrode step 1 in embodiment 1 prepared is as working electrode, and platinum electrode is reference electrode, Ag/
AgCl is reference electrode, is separately added into above-mentioned solution wherein, under-0.75V voltage, and constant voltage enrichment 420s.Then by complete
The electrode becoming enrichment utilizes Differential Pulse Voltammetry (DPV) to measure the peak current of variable concentrations lead ion after being washed with deionized water only
Intensity, the wherein running parameter of Differential Pulse Voltammetry: take-off potential is-0.75V, terminating current potential is-0.2V.
The working curve set up according to step 3 in embodiment 1 calculates plumbum ion concentration, and then calculates the response rate, and result is shown in
Table 1.
Table 1
aParallel five experiments are averaged
Being found out by table 1 data, VOMs/ITO electrode has all obtained good for the mark-on recovery of lead in actual water sample and blood sample
The good response rate.
Embodiment 4
Weighing 50g preserved egg sample, add 100mL pH 5.6 Acetic acid-sodium acetate buffer, stirring in the pasty state, is filtrated to get
Leachate, measures sample respectively by the inventive method and standard atomic absorption spectrometry respectively, compares final result, be shown in Table 2.
Table 2
aParallel five experiments are averaged.
Found out by table 2 data, for the mensuration of preserved egg sample lead content, the inventive method and aas determination
The result obtained is the most identical.
Above example is only the preferred embodiments of the present invention, and not all.Based on the embodiment in embodiment, this
Skilled person is obtained other embodiments on the premise of not making creative work, broadly falls into the protection model of the present invention
Enclose.