CN110333280A - A kind of antimony form electrochemical detection method and its application based on photooxidation - Google Patents
A kind of antimony form electrochemical detection method and its application based on photooxidation Download PDFInfo
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Abstract
The invention discloses based on photooxidation antimony form electrochemical detection method and its application.This method can measure the dissolution peak of trivalent antimony and quinquevalence antimony using anodic stripping voltammetry according to the difference of trivalent antimony and quinquevalence antimony electro-chemical activity respectively under the conditions of different accumulating potentials, and wherein the electrochemical signals of trivalent antimony are not interfered by existing for quinquevalence antimony；Later using trivalent antimony can photooxidation the characteristics of, to sample measured in the form of quinquevalence antimony again after illumination existing for total antimony content, the content of quinquevalence antimony is calculated by minusing in sample.Method process of the invention is simple and reliable, it is small by matrix interference, convenient for operation, and can in same electrolyte solution simultaneously trivalent antimony and pentavalent antimony content are detected.
Description
Technical field
The antimony form electrochemical detection method and its application that the present invention relates to a kind of based on photooxidation, and in particular to Yi Zhongli
Technical field of chemical detection can be belonged to by the antimony form electrochemical detection method of photooxidation characteristic and application with trivalent antimony.
Background technique
Antimony (Sb) is the ninth-largest exploitation metal in the whole world, is widely used in semiconductor, fire retardant, battery and catalyst alloy
Manufacture.Have investigation and shows that antimony has serious harm to human health.It will lead to abdomen for example, being exposed in antimony pollution environment for a long time
Bitterly, diarrhea, dermatitis, the symptoms such as spontaneous abortion and blood pressure raising.Antimony is a type of metal, there is _ III, 0, III and V valence state,
Toxicity and mobility all with antimony that there are valence states is related.Antimony mainly exists in the natural environment with Sb (III) and Sb (V), such as
Sb(OH)3With Sb (OH)6 -.Sb (III) is more stronger than the toxicity of Sb (V), but the mobility of Sb (III) is weaker compared with Sb (V).China's antimony
Reserves occupy first place in the world, and are the maximum antimony in the whole world and its compound products grown place.In recent years, China's antimony pollution outstanding problem,
Water body antimony pollution event takes place frequently, and causes China's water body antimony pollution serious.Develop the detection method of effective antimony content and valence state, energy
It is significant for prevention and Environment control antimony pollution enough as the environmental behaviour beneficial support for deeply probing into antimony.
Being usually used in antimony content and the method for Determination of Different Valence States has the instrument analytical methods such as LC-MS, HG-AFS at present.Electrochemistry inspection
Survey method has easy to operate, and the advantages such as minute is short, testing cost is low are also widely used for various heavy including antimony
The detection of metal is studied.However at present in the electrochemical detection method of antimony, what majority was focused on be by add after excessive reductant with
The macroanalysis that trivalent antimony form is measured, it is less for the Morphology observation concern of antimony, it is primarily due to trivalent antimony electrochemistry
It is active high, and quinquevalence antimony electro-chemical activity is too low, could only detect under strongly acidic conditions, is unfavorable for detecting.Electrochemistry side
Method itself is a kind of instrument miniaturization easy to accomplish, convenient for the method for field assay, for polluting in actual response natural environment
The existing forms of object are highly beneficial, but since electrolyte difference needed for trivalent antimony and quinquevalence antimony detection is too big, do not have always at present
Have realization detection while any chemical reducing agent or oxidant are not added in same solution to trivalent antimony and quinquevalence antimony, this also at
For the technical barrier for hindering electrochemical method detection antimony valence state to develop to in-situ study technology.Therefore a kind of operation letter is developed
Just, high sensitivity, can in same solution not subsequent addition any chemical reagents and while realize trivalent antimony and quinquevalence antimony
Detection, for pushing heavy metal Determination of Different Valence States to play an important role to the development of in-situ study technology.
Summary of the invention
The purpose of the invention is to overcome the shortcomings of that existing detection method can not measure trivalent antimony and quinquevalence antimony simultaneously, mention
For antimony content and the electrochemical detection method of Determination of Different Valence States in a kind of novel water body, this method process is simple and reliable, by matrix
Interfere it is small, convenient for operation, and can in same electrolyte solution simultaneously trivalent antimony and pentavalent antimony content are detected.
The purpose of the present invention is what is be accomplished by the following way:
A kind of antimony form electrochemical detection method based on photooxidation provided by the invention, the specific steps are as follows:
A, the preparation of glass carbon working electrode: first by glass-carbon electrode Al2O3Powder is polished into mirror surface, then successively uses ethyl alcohol, nitre
Acid solution, deionized water be cleaned by ultrasonic respectively after with being dried with nitrogen electrode surface；Then obtained glass-carbon electrode is placed in NaOH
It is scanned with cyclic voltammetry to voltage stabilization in solution；
B, a certain amount of trivalent antimony stock solution or the storage of a certain amount of quinquevalence antimony the preparation of standard solution: are added in electrolytic cell
Standby liquid prepares the trivalent antimony standard solution of various concentration and the pentavalent of various concentration using hydrochloric acid as supporting electrolyte solution respectively
Antimony standard solution；
C, saturation trivalent antimony standard curve determination: the measurement of standard curve: (1) is inserted into the electrolytic cell described in step B
It is prepared in calomel reference electrode (CHI150, Shanghai morning are magnificent), platinum wire auxiliary electrode (CHI115, Shanghai morning are magnificent) and step A
Computer connect with electrochemical workstation, controls the voltage of working electrode by glass carbon working electrode, makes working electrode in -0.4V perseverance
Trivalent antimony under potential condition in enrichment solution, enrichment time 240s, later with square wave voltammetry in -0.4V-0.4V current potential
It is scanned in range, records peak current intensity.Using the concentration of trivalent antimony in the solution of measurement as abscissa, with various concentration pair
The peak current intensity answered is ordinate, draws the standard curve of trivalent antimony, carries out linear fit, obtains standard curve expression formula；
(2) quinquevalence antimony standard curve determination:, saturated calomel reference electrode, platinum filament are inserted into the electrolytic cell described in step B
The glass carbon working electrode prepared in auxiliary electrode and step A, computer is connect with electrochemical workstation, controls working electrode
Voltage makes quinquevalence antimony of working electrode under the conditions of -0.9V constant potential in enrichment solution, enrichment time 180s, then uses square wave
Voltammetry is scanned in -0.8V-0.4V potential range, records peak current intensity；With in the solution of measurement quinquevalence antimony it is dense
Degree is abscissa, using the corresponding peak current intensity of various concentration as ordinate, draws quinquevalence antimony and namely represents in actual sample
The standard curve of total antimony, carries out linear fit, obtains standard curve expression formula.
D, the pre-treatment of practical water body example: water body example is passed through into filtering with microporous membrane, by the suspension in water body example
The impurity such as particulate matter are got rid of；
E, the preparation of the practical water body example of mark-on: in the water body example of step D, it is separately added into a certain amount of trivalent antimony storage
Standby liquid and a certain amount of quinquevalence antimony stock solution are configured to the mark-on sample of known concentration using hydrochloric acid as supporting electrolyte solution；
F, in water body example antimony type and content measurement: by the mark-on sample in step E by side described in step C (1)
Method measures the peak current intensity of trivalent antimony in solution, and electrolytic cell is placed under ultraviolet lamp after the completion of measurement and irradiates 15min, makes sample
Trivalent antimony in product is all oxidized to quinquevalence antimony, then (in sample always by quinquevalence antimony in the measurement solution of method described in step C (2)
Antimony) peak current intensity.Bring the peak current intensity of obtained trivalent antimony peak current intensity and total antimony into step C respectively later
Obtained in trivalent antimony and total antimony standard curve expression formula in, calculate the concentration of trivalent antimony and total antimony in water body example, and
The concentration of quinquevalence antimony in sample is calculated with minusing.
Further, the nitric acid solution concentration is 7.2mol/L, and NaOH solution concentration is 1mol/L, the hydrochloric acid
Concentration is 2.0mol/L.
Further, cyclic voltammetry scanning refers to 4 circle of scanning in -0.5-0.8V voltage range.
Further, the trivalent antimony stock solution is 1mmol/L potassium antimony tartrate, and the quinquevalence antimony stock solution is 1mmol/
L potassium pyroantimonate.
Further, the trivalent antimony standard solution of the various concentration is respectively 0,4 × 10-7、5×10-7、6×10-7、7
×10-7、8×10-7、9×10-7、1×10-6、1.3×10-6、1.5×10-6mol/L；The quinquevalence antimony mark of the various concentration
Quasi- solution is respectively 0,6 × 10-7、7×10-7、8×10-7、9×10-7、1×10-6、1.3×10-6、2×10-6、3×10-6、4
×10-6、5×10-6、7×10-6、1×10-5mol/L。
Further, in the step C, the trivalent antimony in solution is enriched with 240s under -0.4V potential condition, in current potential -
0.1V obtains the oxidation peak of trivalent antimony；Quinquevalence antimony in solution is enriched with 180s under -0.9V potential condition, obtains in current potential -0.1V
To the oxidation peak of quinquevalence antimony i.e. total antimony.
Further, the mark-on sample of the known concentration in the step E contains 0.6 μm of ol/L trivalent antimony, 1.0 μ respectively
Mol/L quinquevalence antimony, 0.6 μm of ol/L trivalent antimony and 0.4 μm of ol/L quinquevalence antimony, 1.0 μm of ol/L trivalent antimonies and 3.0 μm of ol/L quinquevalence antimonies
Four parts of lake water samples and respectively contain 0.6 μm of ol/L trivalent antimony, 2.0 μm of ol/L quinquevalence antimonies, 0.6 μm of ol/L trivalent antimony and 1.4 μ
The seawater sample of mol/L quinquevalence antimony, 1.0 μm of ol/L trivalent antimonies and 6.0 μm of ol/L quinquevalence antimonies.
Further, 15min is irradiated under the ultraviolet lamp in the step F.
It is another object of the present invention to additionally provide a kind of antimony form electrochemical detection method based on photooxidation in water body
Application in antimony form and content detection.
The principle of the present invention is: using the difference of trivalent antimony and quinquevalence antimony electro-chemical activity, using anodic stripping voltammetry,
The dissolution peak of trivalent antimony is first measured under the conditions of different accumulating potentials, wherein the electrochemical signals of trivalent antimony are not existed by quinquevalence antimony
Interference, and under conditions of measuring quinquevalence antimony, there are the interference of trivalent antimony, and the two electro-chemical activity is different, dissolve out overlap of peaks,
Can not accurate quantitative analysis, therefore, the present invention using trivalent antimony can be by photooxidation the characteristics of, to sample carry out illumination after measured again with five
The content of total antimony existing for valence antimony form, the content of quinquevalence antimony is calculated by minusing in sample, is thus determined in sample
The content of trivalent antimony and quinquevalence antimony.
The present invention in solution is the quinquevalence antimony stock solution being directly added into when measuring standard curve, and is to contain in actual sample
There are trivalent antimony and quinquevalence antimony mixture, the antimony after illumination oxidation in sample is all to exist in the form of quinquevalence antimony, so actually
The quinquevalence antimony measured in sample is actually the content of total antimony after photooxidation, therefore to carry out minusing just available practical sample
The content of quinquevalence antimony in product.
In addition, the present invention is not add illumination when measuring standard curve, what is used is all prepared individual three
Valence antimony standard solution or quinquevalence antimony standard solution, and be to need to aoxidize the trivalent antimony in sample by illumination when measuring sample
For the measurement for carrying out total antimony after quinquevalence antimony again.
In step F, it is assumed that the antimony content determined is a, and the content for being actually added into standard sample is b, according to formula r=
A/b × 100% calculates the recovery of standard addition r of trivalent antimony and quinquevalence antimony in sample, and the rate of recovery illustrates this method closer to 100%
It is more reliable.
Saturated calomel reference electrode and platinum wire auxiliary electrode that the present invention uses passes through to be commercially available in the market, is respectively
CHI150 the and CHI115 model of Shanghai Chen Hua Instrument Ltd., the miillpore filter city in the present invention passes through to be bought in the market
By 0.45 μm of water system miillpore filter of Shanghai City new Asia purification device factory production.
The present invention has the advantage that
(1) working electrode preparation process is simple, it is only necessary to polishing and pre-treatment；
(2) test method is simple and efficient, and the detection of trivalent antimony and quinquevalence antimony can be carried out in same solution；
(3) continuous mode utilizes photooxidation trivalent antimony, does not need that any chemical reagents are added；
(4) high sensitivity can be used for the detection such as micro antimony content and valence state in lake water and seawater actual sample.
Detailed description of the invention
Fig. 1 is the schematic diagram of antimony content provided by the invention and valence state detection method.
Fig. 2 is provided for the present invention and is carried out anodic stripping voltammetry in the solution of various concentration trivalent antimony content and total antimony content
Square wave voltammetric scan (SWV) figure and its corresponding standard curve of peak current of detection.
Specific embodiment
Principles and features of the present invention are described with the following Examples, illustrated embodiment is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
A kind of embodiment 1: antimony form electrochemical detection method based on photooxidation
(1) polishing and cleaning of bare glassy carbon electrode: it is the Al of 0.3 μm, 0.05 μm that glass-carbon electrode is successively used to partial size2O3Powder
End is polished into mirror surface, then is successively cleaned by ultrasonic 5min respectively with ethyl alcohol, the nitric acid solution of 7.2mol/L, deionized water, then is used nitrogen
The dry electrode surface of air-blowing；
(2) pretreatment of bare glassy carbon electrode: and then the glass-carbon electrode that step (1) obtains is placed in 1mol/L NaOH solution
In, the first potentiostatic scanning 120s under+1.2V potential condition；The potentiostatic scanning 60s under -0.5V potential condition again；Finally again
It is scanned with cyclic voltammetry to voltage stabilization；
(3) detection of standard items: using the hydrochloric acid of 2.0mol/L as supporting electrolyte solution, preparing trivalent antimony content respectively is
0、4×10-7、5×10-7、6×10-7、7×10-7、8×10-7、9×10-7、1×10-6、1.3×10-6、1.5×10-6mol/L
With pentavalent antimony content be 0,6 × 10-7,7 × 10-7,8 × 10-7,9 × 10-7,1 × 10-6,1.3 × 10-6,2 × 10-6,3 ×
The solution of 10-6,4 × 10-6,5 × 10-6,7 × 10-6,1 × 10-5mol/L, volume are 10mL, obtain trivalent antimony and pentavalent
The standard solution of antimony.The glass carbon working electrode pre-processed, saturation Calomel reference are inserted into the standard solution containing trivalent antimony
Electrode and platinum wire auxiliary electrode, connection electrochemical workstation control, 240s is enriched under -0.4V potential condition, uses square wave later
Voltammetry tests electrolyte solution in -0.4V-0.4V potential range, obtains the oxygen of trivalent antimony in current potential -0.1V or so
Change peak.The peak current for recording various concentration trivalent antimony respectively is drawn as shown in Fig. 2-A, Fig. 2-B according to each gradient peak point current
Standard curve, obtains the standard curve of two sections of trivalent antimonies of low concentration and high concentration, and low concentration is within the scope of 0.4-0.7 μm of ol/L
Linearly, linear equation IpSb(III)(μ A)=5.146CSb(III)(μm ol) -2.0218, R2=0.9855；In high concentration 0.7-
It is linear within the scope of 1.5 μm of ol/L, linear equation IpSb(III)(μ A)=16.8408CSb(III)(μm ol) -10.3229, R2=
0.9992；In the standard solution containing quinquevalence antimony be inserted into pre-processed glass carbon working electrode, saturated calomel reference electrode and
Platinum wire auxiliary electrode, connection electrochemical workstation control, is enriched with 180s under -0.9V potential condition later, uses square wave voltammetry
Electrolyte solution is tested in -0.8V-0.4V potential range, obtains the oxygen of quinquevalence antimony (total antimony) in current potential -0.1V or so
Change peak.The peak current for recording various concentration trivalent antimony respectively is drawn as shown in Fig. 2-C, Fig. 2-D according to each gradient peak point current
Standard curve, obtains the standard curve of low concentration and two sections of high concentration total antimony, and low concentration is in line within the scope of 0.6-1.0 μm of ol/L
Property, linear equation IpSb(V)(μ A)=1.2595CSb(V)(μm ol) -0.6362, R2=0.9929；In high concentration 1.3-10.0 μ
It is linear within the scope of mol/L, linear equation IpSb(V)(μ A)=1.7628CSb(V)(μm ol) -1.6172, R2=0.9994.
(4) detection of minimum detectability: detection method is with (3), and difference is to be added without trivalent antimony and quinquevalence antimony, and detection is empty
It white 20 times, is obtained according to 3 σ rules, the detection of trivalent antimony is limited to 4.21nmol/L, and the detection of total antimony is limited to 5.05nmol/L.
A kind of embodiment 2: application examples of the antimony form electrochemical detection method based on photooxidation of the present invention
Using antimony in a kind of antimony content provided by the invention and valence state detection method detection actual sample fresh water and seawater
Content and valence state.
Taking Beijing's lake water and Shandong Seawater of Jiaozhou Bay sample is actual sample, by actual sample through 0.45 μm of filter membrane mistake
Filter.Filtered lake water sample is divided into four parts, is separately added into 0.6 μm of ol/L trivalent antimony, 1.0 μm of ol/L quinquevalence antimonies, 0.6 μ
Mol/L trivalent antimony and 0.4 μm of ol/L quinquevalence antimony, 1.0 μm of ol/L trivalent antimonies and 3.0 μm of ol/L quinquevalence antimonies；By filtered seawater
Sample is divided into four parts, is separately added into 0.6 μm of ol/L trivalent antimony, 2.0 μm of ol/L quinquevalence antimonies, 0.6 μm of ol/L trivalent antimony and 1.4 μ
Mol/L quinquevalence antimony, 1.0 μm of ol/L trivalent antimonies and 6.0 μm of ol/L quinquevalence antimonies.The dense of 1.67mL 12mol/L is added in electrolytic cell
Hydrochloric acid solution makes concentration of hydrochloric acid 2.0mol/L in sample solution with having added eight parts of samples of target to be diluted to 10mL respectively.Locating
Glass carbon working electrode, saturated calomel reference electrode and the platinum wire auxiliary electrode pre-processed is inserted into the sample solution managed, even
Electrochemical workstation control is connect, 240s is enriched under -0.4V potential condition, later with square wave voltammetry in -0.4V-0.4V current potential
Range tests electrolyte solution, obtains the oxidation peak of trivalent antimony in current potential -0.1V or so；The sample that will have been measured later
Solution, which is placed under ultraviolet lamp, irradiates 15min, and the trivalent antimony in sample is made all to be oxidized to quinquevalence antimony, in the sample that oxidation is completed
Again insertable into glass carbon working electrode, saturated calomel reference electrode and the platinum wire auxiliary electrode pre-processed, connection electrification in solution
Work station control is learned, 180s is enriched under -0.9V potential condition, with square wave voltammetry in -0.8V-0.4V potential range to electrolysis
Matter solution is tested, and obtains the oxidation peak of quinquevalence antimony (total antimony) in current potential -0.1V or so.Eight parts of samples are all provided with the present invention
Method, bring obtained oxidation peak into standard curve expression formula, obtain the content of trivalent antimony and total antimony in solution, be used in combination
Minusing calculates the content of quinquevalence antimony in solution, finally calculates the mark-on reclaims of trivalent antimony and quinquevalence antimony in each sample solution
Rate.By 1 testing result of table it is found that with antimony content provided by the present invention and valence state electrochemical detection method detection lake water and seawater
The average recovery rate of middle trivalent antimony and quinquevalence antimony is 84.5-106.8%, shows antimony content and valence state electrochemistry provided by the invention
Detection method is high to the detection precision of trivalent antimony in lake water and seawater and quinquevalence antimony, as a result accurately and reliably.
1 actual sample TIANZHU XINGNAO Capsul of table
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of antimony form electrochemical detection method based on photooxidation, which is characterized in that this method comprises the following steps:
A, the preparation of glass carbon working electrode: first by glass-carbon electrode Al2O3Powder is polished into mirror surface, then successively molten with ethyl alcohol, nitric acid
Liquid, deionized water be cleaned by ultrasonic respectively after with being dried with nitrogen electrode surface；Then obtained glass-carbon electrode is placed in NaOH solution
It is middle to be scanned with cyclic voltammetry to voltage stabilization；
B, a certain amount of trivalent antimony stock solution or a certain amount of quinquevalence antimony deposit the preparation of standard solution: are added in electrolytic cell
Liquid prepares the trivalent antimony standard solution of various concentration and the quinquevalence antimony of various concentration using hydrochloric acid as supporting electrolyte solution respectively
Standard solution；
C, the measurement of standard curve: (1) trivalent antimony standard curve determination: insertion saturation calomel in the electrolytic cell described in step B
The glass carbon working electrode prepared in reference electrode, platinum wire auxiliary electrode and step A, computer is connect with electrochemical workstation,
The voltage for controlling working electrode, makes trivalent antimony of working electrode under the conditions of -0.4V constant potential in enrichment solution, enrichment time is
240s is scanned in -0.4V-0.4V potential range with square wave voltammetry later, records peak current intensity.With the molten of measurement
The concentration of trivalent antimony draws the standard of trivalent antimony using the corresponding peak current intensity of various concentration as ordinate for abscissa in liquid
Curve carries out linear fit, obtains standard curve expression formula；
(2) saturated calomel reference electrode, platinum filament auxiliary quinquevalence antimony standard curve determination: are inserted into the electrolytic cell described in step B
The glass carbon working electrode prepared in electrode and step A, computer is connect with electrochemical workstation, controls the electricity of working electrode
Pressure, makes quinquevalence antimony of working electrode under the conditions of -0.9V constant potential in enrichment solution, enrichment time 180s, then lied prostrate with square wave
Peace method is scanned in -0.8V-0.4V potential range, records peak current intensity；With the concentration of quinquevalence antimony in the solution of measurement
It draws quinquevalence antimony using the corresponding peak current intensity of various concentration as ordinate for abscissa and namely represents in actual sample always
The standard curve of antimony carries out linear fit, obtains standard curve expression formula.
D, the pre-treatment of practical water body example: water body example is filtered by water system miillpore filter, by the suspension in water body example
The impurity such as particulate matter are got rid of；
E, the preparation of the practical water body example of mark-on: in the water body example of step D, it is separately added into a certain amount of trivalent antimony stock solution
The mark-on sample of known concentration is configured to using hydrochloric acid as supporting electrolyte solution with a certain amount of quinquevalence antimony stock solution；
F, in water body example antimony type and content measurement: the mark-on sample in step E is surveyed by method described in step C (1)
Electrolytic cell is placed under ultraviolet lamp after the completion of measurement and irradiates 10-20min, makes sample by the peak current intensity for determining trivalent antimony in solution
Trivalent antimony in product is all oxidized to quinquevalence antimony, then (in sample always by quinquevalence antimony in the measurement solution of method described in step C (2)
Antimony) peak current intensity.The peak current intensity of obtained trivalent antimony peak current intensity and total antimony is substituted into step C respectively later
Obtained in trivalent antimony and total antimony standard curve expression formula in, calculate the concentration of trivalent antimony and total antimony in water body example, and
The concentration of quinquevalence antimony in sample is calculated with minusing.Assuming that the antimony content determined is a, the content for being actually added into standard sample is
B, the recovery of standard addition r of trivalent antimony and quinquevalence antimony in sample is calculated according to formula r=a/b × 100%, and the rate of recovery is closer
100%, illustrate that this method is more reliable.
2. the antimony form electrochemical detection method according to claim 1 based on photooxidation, which is characterized in that the nitre
Acid solutions are 7.2mol/L, and NaOH solution concentration is 1mol/L, and the concentration of the hydrochloric acid is 2.0mol/L.
3. the antimony form electrochemical detection method according to claim 1 based on photooxidation, which is characterized in that described follows
The scanning of ring voltammetry refers to 4 circle of scanning in -0.5-0.8V voltage range.
4. the antimony form electrochemical detection method according to claim 1 based on photooxidation, which is characterized in that the trivalent
Antimony stock solution is 1mmol/L potassium antimony tartrate, and the quinquevalence antimony stock solution is 1mmol/L potassium pyroantimonate.
5. the antimony form electrochemical detection method according to claim 1 based on photooxidation, which is characterized in that the step
In rapid B, the trivalent antimony standard solution of the various concentration is respectively 0,4 × 10-7、5×10-7、6×10-7、7×10-7、8×
10-7、9×10-7、1×10-6、1.3×10-6、1.5×10-6mol/L；The quinquevalence antimony standard solution of the various concentration is distinguished
It is 0,6 × 10-7、7×10-7、8×10-7、9×10-7、1×10-6、1.3×10-6、2×10-6、3×10-6、4×10-6、5×
10-6、7×10-6、1×10-5mol/L。
6. the antimony form electrochemical detection method according to claim 1 based on photooxidation, which is characterized in that the step
In rapid C, the trivalent antimony in solution is enriched with 240s under -0.4V potential condition, obtains the oxidation peak of trivalent antimony in current potential -0.1V；
Quinquevalence antimony in solution is enriched with 180s under -0.9V potential condition, obtains the oxidation of quinquevalence antimony i.e. total antimony in current potential -0.1V
Peak.
7. the antimony form electrochemical detection method according to claim 1 based on photooxidation, which is characterized in that the step
The mark-on sample of known concentration in rapid E contains 0.6 μm of ol/L trivalent antimony, 1.0 μm of ol/L quinquevalence antimonies, 0.6 μm of ol/L tri- respectively
Four parts of lake water samples of valence antimony and 0.4 μm of ol/L quinquevalence antimony, 1.0 μm of ol/L trivalent antimonies and 3.0 μm of ol/L quinquevalence antimonies and contain respectively
There are 0.6 μm of ol/L trivalent antimony, 2.0 μm of ol/L quinquevalence antimonies, 0.6 μm of ol/L trivalent antimony and 1.4 μm of ol/L quinquevalence antimonies, 1.0 μm of ol/L
The seawater sample of trivalent antimony and 6.0 μm of ol/L quinquevalence antimonies.
8. the antimony form electrochemical detection method according to claim 1 based on photooxidation, which is characterized in that the step
15min is irradiated under ultraviolet lamp in rapid F.
9. the antimony form electrochemical detection method of any of claims 1-8 based on photooxidation is in water body example antimony shape
Application in state and content detection.
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