CN102393413A - Electrode, preparation method thereof and detection method of chemical oxygen demand - Google Patents
Electrode, preparation method thereof and detection method of chemical oxygen demand Download PDFInfo
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- CN102393413A CN102393413A CN2011103399768A CN201110339976A CN102393413A CN 102393413 A CN102393413 A CN 102393413A CN 2011103399768 A CN2011103399768 A CN 2011103399768A CN 201110339976 A CN201110339976 A CN 201110339976A CN 102393413 A CN102393413 A CN 102393413A
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Abstract
The invention provides an electrode which has high sensitivity, short detection time and high detection precision, and a method for detecting COD (Chemical Oxygen Demand) in solution by the electrode. The electrode comprises a substrate and a decorative material wrapped on the surface of the substrate, wherein the decorative material is a titanium dioxide nanoparticle doped with lanthanum oxide. A three-electrode system formed by the electrode detects the COD of the solution to be detected in a short time, and is high in precision and sensitivity.
Description
Technical field
The present invention relates to the Electrochemical Detection field, be specifically related to the detection method of a kind of electrode and preparation method thereof and a kind of COD.
Background technology
Water pollution is one of main environmental pollution, sewage can qualified discharge by the pollution index decision of sewage, wherein one of most important index is COD (chemical oxygen demand the is called for short COD) value of sewage.COD is one of important indicator of weighing the water pollution degree, is meant under certain condition the material concentration (mg/L) of the pairing oxygen of oxygenant that organism or other reducing substanceses are consumed by the strong oxidizer oxidation in the water body.The mensuration of COD is to the safety dumping of industrial waste water and prevent and remedy pollution and have great significance.
The method of traditional mensuration water-quality COD mainly is potassium dichromate oxidation (GB11914-89), and its shortcoming is: analytical cycle is long, and energy dissipation is big, and reagent consumption is many; To use costs such as mercury salt, chromic salts, silver salt high in the analysis, environment is made to be become secondary pollution; If have chlorion, nitrite ion etc. in the solution to be measured, their can with digestive pharmaceutical reaction or and catalyst action, make and measure the result and cause very large deviation.Therefore, seek new method mensuration COD quick, effective, that cost is low, pollution is little and seem particularly important.
In the last few years, the metal oxide photocatalysis oxidation technique had been obtained bigger development, and was more to the research report of the aspects such as preparation, sign, modification, immobilization and the mechanism of action thereof of metal oxide catalysis material both at home and abroad.Wherein titania, environmental friendliness inexpensive because of it, catalytic activity is high, oxidability is strong, good stability, be easy to characteristics such as recovery and enjoy people to favor; The use of optically catalytic TiO 2 technology has been widely used in numerous areas such as wastewater treatment, air purification and virus killing sterilization, and particularly outstanding in the result of use of sewage treatment area.People such as M.R.Hoffman (M.R.Hoffmann, S.T.Martin, W.Choi; D.W.Bahnemann; Environmental Applications of Semiconductor Photocatalysis.Chem.Rev.1995,95, the titania of 69-96.) pointing out to have photocatalytic activity is under optical excitation; Can produce the active oxygen radical a series of strong oxidizers such as (like hydroxyl radical free radicals) with strong oxidizing property, can be nontoxic inorganic molecules with the organic contaminant degree of depth mineralising in the water.Therefore, utilize this principle be expected to realize to organic contaminant fast, The real time measure, for the mensuration of organic contaminant total amount in the water body provides a kind of brand new concept and thinking.More common titanium deoxide catalyst mainly is a titanium dioxide powder at present, and catalytic effect is remarkable under illumination condition.Like people (H.Wang, R.E.Partch, Y.Li, Synthesis of2-Alkylbenzimidazoles via TiO such as Hongyu Wang
2-Mediated Photocatalysis.J.Org.Chem.1997,62,5222-5225.) the powder titanium dioxide photocatalyst is dispersed in benzene-like compounds such as being used for degrading nitrobenzene in the liquid phase.Since normally in liquid phase, the difficult control of degradation process, and be not easy to collect signal, and relying on the concentration difference of measuring the light reaction front and back usually, obvious this method is more coarse.People such as Jin Litong (Jin Litong, Ai Shiyun, Zhang Wen; Li Jiaqing, during aquatic foods jump, Gao Mengnan; Yang Ya, Xu Jiming measures the method for water body chemical requirement with nano-titanium dioxide powder. the patent No.: ZL 02145349.7) invented the water or waste water and a certain amount of inorganic oxide agent solution that in the immersion reactor, add certain amount of nano titanium dioxide powder and certain volume; Be adjusted to certain pH value, constant temperature stirs, after illumination 5-15 minute; Get supernatant after the centrifuging, use spectrophotometry Cr
3+Absorbance calculate the COD value of water or waste water.This method is significantly improved with respect to the chromium method of classics, but whole experiment still is long, and using has highly polluted potassium dichromate, and step is more loaded down with trivial details.Though this powder titanium dioxide can be used for degradation of organic substances on a large scale in solution, powder titanium dioxide is difficult to separate with reaction solution, so the recovery of catalyzer and recycle receive very big restriction.As far as this type light-catalyzed reaction, because particle is dispersed in the solution, its course of reaction is quite complicated; Be difficult to hold its kinetic property and relevant parameter; And experiment condition can only be controlled before reaction beginning, and reaction Once you begin then is difficult to control this experimentation.
Therefore titania is prepared on the electrode, adopts the method for photoelectrocatalysis to test the shortcoming that then can overcome above-mentioned method existence.(D.Jiang, S.Zhang, H.Zhao, Photocatalytic Degradation Characteristics of Different Organic Compounds at TiO such as Australian H.Zhao
2Nanoporous Film Electrodes with Mixed Anatase/Rutile Phases.Environ.Sci.Technol.2007,41,303-308; Zhao Huijun; The Optical Electro-Chemistry of COD detects. and Chinese application number: it doesn't matter in 200480009324.6 mandates here; As long as can find) be fixed on synthetic titanium dioxide nano-particle on the conductive substrates like tin indium oxide (ITO) electrode of making on glass; Carry out the photoelectrocatalysis reaction, degradation of organic substances, the COD value of mensuration sewage.This method can be separated catalyzer easily with reactant liquor, can recycle catalyzer.Owing to adopted the photoelectricity coupling technique, impressed voltage has effectively suppressed the compound of light induced electron and photohole, and the light induced electron that illumination produces down can be shifted by electrode effectively, can improve catalytic efficiency significantly.Zhou Baoxue etc. (photoelectrocatalysis is measured the method for COD for Zhou Baoxue, the Cai Wei people. the patent No.: ZL 200510026210.9) and with the metallic titanium matrix surface TiO
2Nano-pipe array thin film is a photocatalyst, the coulomb electric charge pH-value determination pH COD value through the organism photoelectrocatalysioxidization oxidization of measuring water sample in the thin layer microreactor when complete.But owing to shortcomings such as pure titania bandwidth is bigger, and the thickness of electronics-hole easy compound and thin layer microreactor is little have restricted its practical application.
Summary of the invention
It is a kind of highly sensitive that the technical matters that the present invention will solve is to provide, and detection time is short, the electrode that accuracy of detection is high and with the method for COD value in the said electrode detection solution.
In order to solve above technical matters, the invention provides a kind of electrode, the decorative material that comprises substrate and be wrapped in said substrate surface; Wherein, said decorative material is the titanium dioxide nano-particle that lanthanum sesquioxide mixes.
Preferably, the molar percentage x that lanthanum sesquioxide accounts for titanium dioxide nano-particle in the said decorative material meets the following conditions: 0.5%≤x≤5%.
Preferably, said substrate is an indium oxide tin glass.
The present invention also provides a kind of preparation method of electrode, comprising:
Substrate is provided;
Butyl titanate is mixed with ethanol, diacetone, obtain first solution;
Lanthanum sesquioxide is mixed with hydrochloric acid and ethanol, obtain second solution;
Said substrate is soaked in the mixed solution of said first solution and second solution, and, in said substrate, coats said mixed solution through solution-gel method and czochralski method;
Said substrate is taken out from said mixed solution, and sintering obtains electrode.
Preferably, the mol ratio of said lanthanum sesquioxide and said butyl titanate is (0.5～5): (95～100).
Preferably, said sol-gel process and czochralski method coat said mixed solution and are specially in said substrate:
Said substrate is immersed in the said mixed solution, stop 20～50min, the speed with 40～80mm/s lifts said substrate then;
With the aging at ambient temperature 6-20h of the said substrate that from mixed solution, lifts out.
Preferably, said sintering is specially:
Said substrate after aging is warming up to 400～600 ℃ with the speed program of 1-5 ℃/min, heats up and be incubated 1～16h.
The present invention also provides a kind of detection method of chemical oxygen level, comprising:
A) with the described electrode of claim 1 as working electrode, platinum electrode is as to electrode, the Ag/AgCl electrode is supporting electrolyte as contrast electrode with the inorganic salts that do not have photoelectric activity;
B) on said working electrode, apply voltage, with the said working electrode of UV-irradiation, first current value in the record electrolyte;
C) standard solution that detects different COD values successively under UV-irradiation, second current value that obtains;
D) do typical curve according to the difference of first current value and second current value with corresponding COD value;
E) detect three current value of testing sample under UV-irradiation, on said typical curve, find the pairing COD value of difference of the 3rd current value and first current value, be the COD value of testing sample.
Preferably, step c) is specially:
C1) add successively that the COD value is respectively 5,10,20,50,100,150, the standard solution by Potassium Hydrogen Phthalate (KHP) or glucose or the preparation of COD national standard appearance of 200mg/L;
Photocurrent when c2) being recorded in the UV-irradiation working electrode respectively.
Preferably, the said inorganic salts that do not have photoelectric activity are NaNO
3, Na
2SO
4
Electrode provided by the invention is substrate with tin indium oxide (ITO) electrode preferably, adopts sol-gel process and czochralski method, after calcining, is prepared into the electrode that lanthanum sesquioxide doping titanium dioxide nano particle is modified.Can overcome the shortcoming of prior art.Through the photoelectric-synergetic catalysis all kinds of organic contaminants of degrading effectively.Because material is accomplished that on the ITO electro-conductive glass, the preparation process is simple, but the electrode recycled for multiple times, and having overcome is that fine catalyst is difficult to shortcomings such as solution separating after use in the suspension system of photocatalyst with the titania powder.And, can improve the photoelectrocatalysis performance of titania through rare earth doped La.Electrode production process is simple, and material is cheap, and electrode specific surface area is big, and the life-span is long, and catalytic activity is high; Electrode is firm, surface-stable, good conductivity; Photoelectrocatalysis is measured the time short (only 3～5 minutes) of COD process, does not need high temperature, does not use the oxygenant that brings secondary pollution etc., environmental friendliness.In addition, can be so that course of reaction to be controlled and signal collection is more or less freely, response is fast; Efficient is higher; Simple to operate, the range of linearity is wide, and is highly sensitive; Measure that COD value is low to be reached 5mg/L and be than the detection method of using in the national standard that COD value that potassium dichromate method is measured is hanged down minimum 30mg/L lower, explain that detection sensitivity is higher.Can fast and effeciently measure all kinds of actual water sample COD values through the Optical Electro-Chemistry method.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that these just restriction for further specifying feature and advantage of the present invention rather than patent of the present invention being required is described.
The invention provides a kind of electrode, the decorative material that comprises substrate and be wrapped in said substrate surface; Wherein, said decorative material is the titanium dioxide nano-particle that lanthanum sesquioxide mixes.
Though the electrode that the ITO substrate preparation that the nano titanium oxide that uses in the prior art is modified becomes has good effect on photoelectrocatalysis detects; But; The broader bandwidth of titanium dioxide nano-particle itself, when modifying, the crystal grain of titania is growth constantly; Make hole and electron pair compound, make and detect the electric current shakiness.Be not easy to the detection of COD value in the solution of small concentration, error is bigger.And because the 4f orbital electron underfill of rare-earth elements La, so it can form compound with lewis base.So with La
2O
3Be doped to TiO
2The electrode that middle preparation lanthanum sesquioxide doping titanium dioxide nano particle is modified, La
2O
3Introducing can suppress TiO
2Grain growth; Suppress the anatase transformation of rutile phase in opposite directions, it is big that the surface oxygen room contains quantitative change, right compound in light induced electron and hole in the time of effectively reducing photoelectrocatalysis; And help the absorption of organism, thereby improve the photoelectrocatalysis performance of titania on the surface.
According to the present invention, said substrate is preferably tin indium oxide (ITO) glass, has good electric conductivity, is prone to modify.The titanium dioxide nano-particle that on said indium oxide tin glass, has lanthanum sesquioxide to mix, the molar percentage x that lanthanum sesquioxide accounts for titanium dioxide nano-particle in the said decorative material preferably meets the following conditions: 0.5%≤x≤5%.More preferably: 1%≤x≤3%.Doping is unsuitable excessive, otherwise can influence the character of titanium dioxide nano-particle.
According to the present invention, the preparation method of said electrode is:
Substrate is provided;
Butyl titanate is mixed with ethanol, diacetone, obtain first solution;
Lanthanum sesquioxide is mixed with hydrochloric acid and ethanol, obtain second solution;
Said substrate is soaked in the mixed solution of said first solution and second solution, and, in said substrate, coats said mixed solution through solution-gel method and czochralski method;
Said substrate is taken out from said mixed solution, and sintering obtains electrode.
Be specially:
1). the ITO electrode that cuts is cleaned the ITO electrode that obtains handling well with washing agent, resistivity successively successively greater than ultrapure water and the ITO cleaning fluid of 18.2M Ω .cm.
2). with slowly splashing in the 30-50mL ethanol in the 10-30mL butyl titanate solution, magnetic agitation 5-30min adds the 0.5-5mL diacetone, stirs 5-30min, obtains first solution.Accurately take by weighing a certain amount of La
2O
3Powder, and be dissolved in the hydrochloric acid of 6-30mL 6mol/L, magnetic agitation adds the 10-30mL absolute ethyl alcohol after dissolving extremely fully, and magnetic agitation 5-30min obtains second solution.Under the magnetic agitation, second solution is slowly splashed in first solution, all drip off general 30-60min, stir 2-8h, obtain yellow solution.The ITO electro-conductive glass that cleans up is immersed in the said solution, stop 20-50min, the speed with 40-80mm/s lifts up then.With the ITO electro-conductive glass at ambient temperature, aging 6-20h.At last the ITO electro-conductive glass is put into muffle furnace, be warming up to 400～600 ℃ with the speed program of 1-5 ℃/min, the time is after 1～16h is cooled to room temperature, and cooled electrode is preferably lifted and sintering 1～2 time again, obtains La
2O
3/ TiO
2Electrode.The sample La that makes
2O
3Doping and TiO
2Molar percentage (being designated hereinafter simply as the La doping) be 0.5%-5% (mole fraction).
The present invention also provides the detection method of a kind of COD, comprising:
A) with the described electrode of claim 1 as working electrode, platinum electrode is as to electrode, the Ag/AgCl electrode is formed three-electrode system as contrast electrode, is supporting electrolyte with the inorganic salts that do not have photoelectric activity;
B) on said working electrode, apply voltage, with the said working electrode of UV-irradiation, first current value in the record electrolyte;
C) standard solution that detects different COD values successively under UV-irradiation, second current value that obtains;
D) do typical curve according to the difference of first current value and second current value with corresponding COD value;
E) detect three current value of testing sample under UV-irradiation, on said typical curve, find the pairing COD value of difference of the 3rd current value and first current value, be the COD value of testing sample.
Be specially:
The present invention adopts three-electrode system, is modified to working electrode with the lanthanum sesquioxide doping titanium dioxide nano particle for preparing, and platinum electrode is to electrode, and Ag/AgCl (saturated KCl) electrode is a contrast electrode, NaNO
3, Na
2SO
4The inorganic salts that do not have photoelectric activity are supporting electrolyte; Adopt CHI electro-chemical systems etc. on working electrode, apply+0.1～+ voltage of 0.8V, when the UV-irradiation working electrode, write down the photocurrent I of blank supporting electrolyte
o, add successively that the COD value is respectively 5,10,20,50,100,150, the standard solution by Potassium Hydrogen Phthalate (KHP) or glucose or the preparation of COD national standard appearance of 200mg/L, and the photocurrent I when being recorded in the UV-irradiation working electrode respectively
c, the I of variable concentrations COD value
cDeduct blank photocurrent I respectively
oObtain photocurrent variations value Δ I
c=I
c-I
o, corresponding its COD value mapping obtains typical curve.The actual sample of unknown COD concentration directly or after the dilution is joined in the electrolytic cell photocurrent I during record UV-irradiation working electrode
x, deduct I
oBack photocurrent variations value Δ I
xBe the COD value of sample or the COD value after the dilution in COD value corresponding on the typical curve.
The lanthanum sesquioxide doping titanium dioxide nano particle modified electrode of the present invention's preparation can realize easily to surface water that chemical plant, food factory, chemical plant, sewage treatment plant etc. go out the COD value of water sample and carry out Optical Electro-Chemistry mensuration.The electrode environmental protection of the present invention's preparation, the life-span is long, can repeatedly use, and is simple to operate, good stability, highly sensitive, in addition, this electrode pair The pretreatment requirement is very low, detection is quick, cost is low, is suitable for routine analysis.
Below be specific embodiment of the present invention, set forth the present invention program in detail.
Embodiment 1
With the lanthanum doping for preparing is that 1% lanthanum sesquioxide doping titanium dioxide nano particle modified electrode is used for photoelectric catalysis degrading glucose, 0.01M NaNO
3For supporting electrolyte is a blank solution, write down the photocurrent I of blank supporting electrolyte when adopting CHI830B electrochemical analyser (Shanghai occasion China) on working electrode, to apply constant potential, the UV-irradiation working electrode of 0.3V
o, add successively that the COD value is respectively 5,10,20,50,100,150, the glucose solution of 200mg/L, the photocurrent I of record UV-irradiation working electrode
c, the photocurrent variations value Δ I of the glucose solution of different COD values when calculating UV-irradiation
c=I
c-I
o, obtain calibration curve thus.Calibration curve obtains sewage disposal plant effluent COD value and carries out correlation calculations with the COD value that adopts GB potassium dichromate oxidation (GB 11914-89) to obtain thus; Both have good consistance as a result, explain that this method can be used for the mensuration of sewage disposal plant effluent COD.
Embodiment 2
With the lanthanum doping for preparing is that 0.5% lanthanum sesquioxide doping titanium dioxide nano particle modified electrode is used for the photoelectric catalysis degrading Potassium Hydrogen Phthalate, 0.01M NaNO
3For supporting electrolyte is a blank solution, write down the photocurrent I of blank supporting electrolyte when adopting CHI830B electrochemical analyser (Shanghai occasion China) on working electrode, to apply constant potential, the UV-irradiation working electrode of 0.1V
o, add successively that the COD value is respectively 5,10,20,50,100,150, the Potassium Hydrogen Phthalate solution of 200mg/L, the photocurrent I of record UV-irradiation working electrode
c, the photocurrent variations value Δ I of the Potassium Hydrogen Phthalate solution of different COD values when calculating UV-irradiation
c=I
c-I
o, obtain calibration curve thus.Calibration curve obtains the water outlet COD of food factory value and carries out correlation calculations with the COD value that adopts GB potassium dichromate oxidation (GB 11914-89) to obtain thus, and both have good consistance as a result, explain that this method can be used for the mensuration of the water outlet COD of food factory.
Embodiment 3
With the lanthanum doping for preparing is that 2% lanthanum sesquioxide doping titanium dioxide nano particle modified electrode is used for the photoelectric catalysis degrading Potassium Hydrogen Phthalate, 0.02M Na
2SO
4For supporting electrolyte is a blank solution, write down the photocurrent I of blank supporting electrolyte when adopting CHI830B electrochemical analyser (Shanghai occasion China) on working electrode, to apply constant potential, the UV-irradiation working electrode of 0.5V
o, add successively that the COD value is respectively 5,10,20,50,100,150, the Potassium Hydrogen Phthalate solution of 200mg/L, the photocurrent I of record UV-irradiation working electrode
c, the photocurrent variations value Δ I of the Potassium Hydrogen Phthalate solution of different COD values when calculating UV-irradiation
c=I
c-I
o, obtain calibration curve thus.Calibration curve obtains medicine plant effluent COD value and carries out correlation calculations with the COD value that adopts GB potassium dichromate oxidation (GB 11914-89) to obtain thus, and both have good consistance as a result, explain that this method can be used for the mensuration of medicine plant effluent COD.
Embodiment 4
With the lanthanum doping for preparing is that 3% lanthanum sesquioxide doping titanium dioxide nano particle modified electrode is used for photoelectric catalysis degrading COD national standard appearance, 0.01M NaNO
3For supporting electrolyte is a blank solution, write down the photocurrent I of blank supporting electrolyte when adopting CHI830B electrochemical analyser (Shanghai occasion China) on working electrode, to apply constant potential, the UV-irradiation working electrode of 0.3V
o, add successively that the COD value is respectively 20,50,100,150, the COD national standard appearance of 200mg/L, the photocurrent I of record UV-irradiation working electrode
c, the photocurrent variations value Δ I of the COD national standard appearance of different COD values when calculating UV-irradiation
c=I
c-I
o, obtain calibration curve thus.Calibration curve obtains the water outlet COD of food factory value and carries out correlation calculations with the COD value that adopts GB potassium dichromate oxidation (GB 11914-89) to obtain thus, and both have good consistance as a result, explain that this method can be used for the mensuration of the water outlet COD of food factory.
Embodiment 5
With the lanthanum doping for preparing is that 5% lanthanum sesquioxide doping titanium dioxide nano particle modified electrode is used for photoelectric catalysis degrading glucose, 0.02M NaNO
3For supporting electrolyte is a blank solution, write down the photocurrent I of blank supporting electrolyte when adopting CHI830B electrochemical analyser (Shanghai occasion China) on working electrode, to apply constant potential, the UV-irradiation working electrode of 0.8V
o, add successively that the COD value is respectively 5,10,20,50,100,150, the glucose solution of 200mg/L, the photocurrent I of record UV-irradiation working electrode
c, the photocurrent variations value Δ I of the glucose solution of different COD values when calculating UV-irradiation
c=I
c-I
o, obtain calibration curve thus.Calibration curve obtains sewage disposal plant effluent COD value and carries out correlation calculations with the COD value that adopts GB potassium dichromate oxidation (GB 11914-89) to obtain thus; Both have good consistance as a result, explain that this method can be used for the mensuration of sewage disposal plant effluent COD.
More than the detection method of a kind of electrode provided by the invention and preparation method thereof and a kind of COD has been carried out detailed introduction; Having used concrete example among this paper sets forth principle of the present invention and embodiment; The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. an electrode is characterized in that, the decorative material that comprises substrate and be wrapped in said substrate surface; Wherein, said decorative material is the titanium dioxide nano-particle that lanthanum sesquioxide mixes.
2. electrode according to claim 1 is characterized in that, the molar percentage x that lanthanum sesquioxide accounts for titanium dioxide nano-particle in the said decorative material meets the following conditions: 0.5%≤x≤5%.
3. electrode according to claim 1 is characterized in that, said substrate is an indium oxide tin glass.
4. the preparation method of an electrode is characterized in that, comprising:
Substrate is provided;
Butyl titanate is mixed with ethanol, diacetone, obtain first solution;
Lanthanum sesquioxide is mixed with hydrochloric acid and ethanol, obtain second solution;
Said substrate is soaked in the mixed solution of said first solution and second solution, and, in said substrate, coats said mixed solution through solution-gel method and czochralski method;
Said substrate is taken out from said mixed solution, and sintering obtains electrode.
5. preparation method according to claim 4 is characterized in that, the mol ratio of said lanthanum sesquioxide and said butyl titanate is (0.5～5): (95～100).
6. preparation method according to claim 4 is characterized in that, said sol-gel process and czochralski method coat said mixed solution and be specially in said substrate:
Said substrate is immersed in the said mixed solution, stop 20～50min, the speed with 40～80mm/s lifts said substrate then;
With the aging at ambient temperature 6-20h of the said substrate that from mixed solution, lifts out.
7. preparation method according to claim 4 is characterized in that, said sintering is specially:
Said substrate after aging is warming up to 400～600 ℃ with the speed program of 1-5 ℃/min, heats up and be incubated 1～16h.
8. the detection method of a chemical oxygen level is characterized in that, comprising:
A) with the described electrode of claim 1 as working electrode, platinum electrode is as to electrode, the Ag/AgCl electrode is formed three-electrode system as contrast electrode, is supporting electrolyte with the inorganic salts that do not have photoelectric activity;
B) on said working electrode, apply voltage, with the said working electrode of UV-irradiation, first current value in the record electrolyte;
C) standard solution that detects different COD values successively under UV-irradiation, second current value that obtains;
D) do typical curve according to the difference of first current value and second current value with corresponding COD value;
E) detect three current value of testing sample under UV-irradiation, on said typical curve, find the pairing COD value of difference of the 3rd current value and first current value, be the COD value of testing sample.
9. detection method according to claim 8 is characterized in that step c) is specially:
C1) add successively that the COD value is respectively 5,10,20,50,100,150, the standard solution by Potassium Hydrogen Phthalate (KHP) or glucose or the preparation of COD national standard appearance of 200mg/L;
Photocurrent when c2) being recorded in the UV-irradiation working electrode respectively.
10. detection method according to claim 8 is characterized in that, the said inorganic salts that do not have photoelectric activity are NaNO
3, Na
2SO
4
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| CN109887646A (en) * | 2019-03-08 | 2019-06-14 | 宁波石墨烯创新中心有限公司 | A kind of electrode and preparation method thereof |
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