CN1696684A - Photoelectrocatalysis method for determining chemical oxygen demand - Google Patents
Photoelectrocatalysis method for determining chemical oxygen demand Download PDFInfo
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- CN1696684A CN1696684A CN 200510026210 CN200510026210A CN1696684A CN 1696684 A CN1696684 A CN 1696684A CN 200510026210 CN200510026210 CN 200510026210 CN 200510026210 A CN200510026210 A CN 200510026210A CN 1696684 A CN1696684 A CN 1696684A
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Abstract
A method of using photoelectric catalysis to detect chemical oxygen demand includes carrying out photoelectric catalytic reaction in a thin microreactor, using Ti as positive electrode, using TiO2 nanotube array film on metal Ti as light catalyst, using metal Pt as pair electrode and Ag / Ag CI as reference electrode, using inert inorganic salt as electrolyte, determining COD value by measuring Coulomb electricity value at time when organic substance of water sample in reactor is totally catalyzed and oxidized.
Description
Technical field
The present invention relates to a kind of photoelectrocatalysis and measure the method for chemical oxygen demand (COD), relate in particular to a kind of TiO of utilization
2Nanometer pipe array electrode carries out the method that photoelectrocatalysis is measured water-quality COD (chemical oxygen demand (COD)), belongs to the environmental monitoring technology field.
Background technology
At present, the COD method for measuring mainly contains standard law (that is potassium dichromate method), coulometry and photometry.These methods need to consume a large amount of potassium dichromate, the concentrated sulphuric acid and expensive silver sulfate mostly in operating process, simultaneously in order to eliminate the interference of chlorion, also needing to add the great toxicity mercuric sulfate is sheltered, and need high temperature to clear up, return time is long, and operating process is loaded down with trivial details, and minute reaches 2～4 hours, the measurement result poor accuracy also pollutes environment.In recent years, in order to address the above problem, many new COD assay methods had appearred.Chinese invention patent (application number 02145349.7) " measures the method for chemical oxygen demand of water body with nano-titanium dioxide powder " and Chinese invention patent (application number 200410015761.0) " detects the method for chemical oxygen demand of water body ", in the reaction system of measuring COD, introduced nano titanium dioxide photocatalyst, shortened minute greatly, but in reaction system, still kept the potassium dichromate oxidation reaction system, failed to eliminate the pollution problem of chromic salts in the COD mensuration.Chinese invention patent (application number 02111970.8) discloses a kind of " nano COD sensor, preparation and uses thereof ", and this is invented with PbO
2Modified electrode is measured COD as working electrode by the method for catalytic oxidation, and this method minute is short, measurement range is wide, and Without Chrome Salt, mercury salt pollute and do not use expensive silver sulfate, but this method is at PbO
2Cause the big heavy metal lead of toxicity to pollute in the preparation of electrode, use, reparation and the discarded process easily.
In recent years, the method for utilizing the photoelectrocatalysis principle to measure organic concentration in the oxidation of electrode surface catalyzing organic is developed.People such as Zhao Hui jun were at " Analytica Chemica Acta " 2004 in 2004,514:89-97 " Photoelectrochemical determination of chemical oxygendemand based on an exhaustive degradation model in a thin-layer cell " and " Analytical Chemistry " 2004, reported among the 76:155-160 " Development of a directphotoelectrochemical method for determination of chemical oxygen demand " and utilized the nano-titanium dioxide film electrode, by the method for photoelectrocatalysioxidization oxidization reaction assay COD as anode.Owing to does not have poisonous, harmful reagent in this assay method, thereby fundamentally solved the pollution problem in the COD mensuration, but the photoelectrocatalysis working electrode anode that this assay method uses is by conductive glass surface deposition (coating) nano-TiO
2The method of film obtains, and this film is the preparation process complexity not only, and adhesion is low between film and the electro-conductive glass, and film ftractures easily, comes off, and the electron transport resistance is big in the film, and the photoelectrocatalysis reaction efficiency is low, thereby has influenced the stability of method.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, the method that provides a kind of photoelectrocatalysis to measure chemical oxygen demand (COD), method is simple to be realized easily, can stablize, carry out accurately COD mensuration in the water sample, and can not pollute environment.
For realizing this purpose, the present invention utilizes TiO
2Nanometer pipe array electrode carries out photoelectrocatalysis and measures water-quality COD, is anode with the Titanium, with the metallic titanium matrix surface TiO
2Nano-pipe array thin film is a photocatalyst, and the enclosed pasture charge value by the organism photoelectrocatalysioxidization oxidization of measuring water sample in the thin layer microreactor when complete is measured the COD value.
Concrete grammar of the present invention is: the photoelectrocatalysis of measuring COD is reflected in the skim microreactor and carries out, and thin layer microreactor separation is 0.1～0.2mm, and every side channel wall area is 0.7～2cm in the groove
2, be anode with the Titanium, with metallic titanium matrix surface last layer TiO
2Nano-pipe array thin film is a photocatalyst, metal platinum (as platinum gauze) is done electrode, Ag/AgCl does contrast electrode, with inert inorganic salt such as sodium nitrate etc. is electrolyte, in the thin layer microreactor, inject different COD standard solution, apply bias-voltage 0.3～0.5V on anode, simultaneously ultraviolet light exposes to TiO in the opposite side cell wall by the quartz window of reserving on the side channel wall
2On the nano-pipe array thin film, the coulomb electric charge value that is consumed when reading the complete photoelectrocatalysioxidization oxidization of organism at regular intervals, parallel carrying out 3 times, get the response curve of coulomb electric charge value and COD, under identical working curve, when measuring the COD value of water sample, only need directly to get COD value in the water outlet according to enclosed pasture electric weight reading value.
TiO of the present invention
2Nano-pipe array thin film can be prepared by metal titanium sheet anodic oxidation in containing the aqueous solution of hydrofluorite, high temperature sintering, it is characterized in that this film and Titanium base conductor are integrated.
TiO of the present invention
2The caliber of its nanotube of nano-pipe array thin film is in 20～90nm scope.
TiO of the present invention
2Nano-pipe array thin film also can be via publicly-owned TiO
2TiO after film modified technology is modified
2Nano-pipe array thin film, these publicly-owned TiO
2Film modified technology can be TiO
2Film thin surface noble metal loading technology or anion doped technology or cation doping technology.
The present invention adopts the nano-tube array film electrode photoelectrocatalysis to measure chemical oxygen demand (COD), compared with the prior art has significant advantage.Because the working electrode Titanium and the photocatalyst TiO that use in the assay method
2Nano-pipe array thin film is integrated, in conjunction with firmly, good conductivity, stability be high, helps separating of electronics and hole in the photoelectrocatalysis process, helps oxidation of organic compounds up hill and dale, thereby COD accuracy of measurement height.Method of the present invention can fundamentally solve the pollution problem in the COD mensuration.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described, but do not constitute limitation of the invention.
Embodiment 1:
The photoelectrocatalysis of measuring COD is reflected in the skim microreactor and carries out, and makes anode with Titanium, and the caliber of titanium matrix surface is about 60～90nm, pipe range 400nm left and right sides TiO
2Nano-pipe array thin film is a photocatalyst, and the metal platinum silk screen is done electrode, and Ag/AgCl does contrast electrode, and thin layer microreactor separation is 0.1mm, every side channel wall area 0.7cm in the groove
2, be electrolyte with sodium nitrate, in the thin layer microreactor, inject different COD standard solution, on anode, apply bias-voltage 0.3V, ultraviolet light exposes to TiO in the opposite side cell wall by the quartz window of reserving on the side channel wall simultaneously
2On the nano-pipe array thin film, the coulomb electric charge value that is consumed when reading the complete photoelectrocatalysioxidization oxidization of organism every 3 minutes, parallel carrying out 3 times, the response curve of coulomb electric charge value and COD, working curve coefficient R=0.9928.Under identical working curve, measure certain sanitary wastewater COD value and be 109mg/L.
Embodiment 2:
The photoelectrocatalysis of measuring COD is reflected in the skim microreactor and carries out, and makes anode with Titanium, and the caliber of titanium matrix surface is about 20～40nm, pipe range 600nm left and right sides TiO
2Nano-pipe array thin film is a photocatalyst, and the metal platinized platinum is cooked electrode, and Ag/AgCl does contrast electrode, and thin layer microreactor separation is 0.2mm, every side channel wall area 0.2cm in the groove
2, be electrolyte with sodium nitrate, in the thin layer microreactor, inject different COD standard solution, on anode, apply bias-voltage 0.5V, ultraviolet light exposes to TiO in the opposite side cell wall by the quartz window of reserving on the side channel wall simultaneously
2On the nano-pipe array thin film, the coulomb electric charge value that is consumed when reading the complete photoelectrocatalysioxidization oxidization of organism every 5 minutes, parallel carrying out 3 times, the response curve of coulomb electric charge value and COD, working curve coefficient R=0.9923.Under identical working curve, measure certain river COD value and be 12.3mg/L.
Embodiment 3:
The photoelectrocatalysis of measuring COD is reflected in the skim microreactor and carries out, and makes anode with Titanium, and the caliber of titanium matrix surface is about 40～60nm, pipe range 500nm left and right sides TiO
2Nano-pipe array thin film is a photocatalyst, and the metal platinum silk screen is done electrode, and Ag/AgCl does contrast electrode, and thin layer microreactor separation is 0.1mm, every side channel wall area 0.9cm in the groove
2, be electrolyte with sodium sulphate, in the thin layer microreactor, inject different COD standard solution, on anode, apply bias-voltage 0.3V, ultraviolet light exposes to TiO in the opposite side cell wall by the quartz window of reserving on the side channel wall simultaneously
2On the nano-pipe array thin film, the coulomb electric charge value that is consumed when reading the complete photoelectrocatalysioxidization oxidization of organism every 3 minutes, parallel carrying out 3 times, the response curve of coulomb electric charge value and COD, working curve coefficient R=0.9935.Under identical working curve, measure certain D/W COD value and be 197mg/L.
Embodiment 4:
According to embodiment 3, by vacuum gas phase heat deposition at titanium base TiO
2The thick Pt of nano-pipe array thin film surface deposition one deck 5nm gets platinum depositing Ti O
2Nano-pipe array thin film is a photocatalyst with this film, and other condition is with embodiment 3, the coulomb electric charge value that is consumed when reading the complete photoelectrocatalysioxidization oxidization of organism every 2 minutes, parallel carrying out 3 times, the response curve of coulomb electric charge value and COD, working curve coefficient R=0.9937.Under identical working curve, the COD value of measuring certain compound probability waste water is 78mg/L.
Claims (4)
1, a kind of photoelectrocatalysis is measured the method for chemical oxygen demand (COD), it is characterized in that: the photoelectrocatalysis of measuring COD is reflected in the skim microreactor and carries out, and thin layer microreactor separation is 0.1～0.2mm, every side channel wall area 0.7～2cm in the groove
2, be anode with the Titanium, with the metallic titanium matrix surface TiO
2Nano-pipe array thin film is a photocatalyst, and metal platinum is to electrode, and Ag/AgCl is a contrast electrode, is electrolyte with the inert inorganic salt, and the anode bias-voltage is 0.3～0.5V, and ultraviolet light exposes to TiO in the opposite side cell wall by the quartz window of reserving on the side channel wall
2On the nano-pipe array thin film, the enclosed pasture charge value by the organism photoelectrocatalysioxidization oxidization of measuring water sample in the thin layer microreactor when complete is determined the COD value.
2, measure the method for chemical oxygen demand (COD) according to the photoelectrocatalysis of claim 1, it is characterized in that described TiO
2Nano-pipe array thin film is prepared by metal titanium sheet anodic oxidation in containing the aqueous solution of hydrofluorite, high temperature sintering, and this film and Titanium base conductor are integrated.
3, measure the method for chemical oxygen demand (COD) according to the photoelectrocatalysis of claim 1, it is characterized in that described TiO
2The nanotube caliber of nano-pipe array thin film is in 20～90nm scope.
4, measure the method for chemical oxygen demand (COD) according to the photoelectrocatalysis of claim l, it is characterized in that described TiO
2Nano-pipe array thin film is via TiO
2TiO after film modified technology is modified
2Nano-pipe array thin film, these TiO
2Film modified technology is TiO
2Film thin surface noble metal loading technology or anion doped technology or cation doping technology.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007016740A1 (en) * | 2005-08-11 | 2007-02-15 | Aqua Diagnostic Pty. Ltd. | Water analysis using a photoelectrochemical method |
| CN100404123C (en) * | 2006-08-01 | 2008-07-23 | 华东师范大学 | Capillary tube array photo catalysis reactor and its preparation and application |
| CN100429500C (en) * | 2006-06-13 | 2008-10-29 | 山东海信环保有限公司 | Method for detecting chemical oxygen demand of water body |
| CN101105472B (en) * | 2007-06-11 | 2010-05-19 | 大连理工大学 | Water body chemical oxygen demand electrochemical measuring method |
| CN101221146B (en) * | 2008-01-31 | 2010-10-27 | 上海交通大学 | Method for measuring chemical oxygen demand by TiO2 nano hole array electrode photoelectrocatalysis |
| CN102706945A (en) * | 2011-03-28 | 2012-10-03 | 同济大学 | Method for determining waster water COD by simulating sunlight photoelectrocatalysis |
| CN102866186A (en) * | 2012-09-12 | 2013-01-09 | 合肥工业大学 | Circulating-type water chemical oxygen demand detection photoelectrochemical sensor |
| CN103604847A (en) * | 2013-12-06 | 2014-02-26 | 中国科学技术大学 | Photocoupling method for determining chemical oxygen demand in water body |
| CN104316581A (en) * | 2014-10-23 | 2015-01-28 | 华南理工大学 | Visible light photoelectrocatalysis based COD (chemical oxygen demand) sensor and preparation method and application thereof |
| CN105510423A (en) * | 2015-12-29 | 2016-04-20 | 南京洁态环保科技有限公司 | Automatic on-line monitor for measuring water body COD (chemical oxygen demand) |
| CN106596838A (en) * | 2016-11-23 | 2017-04-26 | 深圳市朗石科学仪器有限公司 | COD measuring method |
| CN107941731A (en) * | 2017-12-05 | 2018-04-20 | 海南聚能科技创新研究院有限公司 | COD on-line detector in a kind of water quality |
| CN110596208A (en) * | 2019-09-04 | 2019-12-20 | 东华大学 | Method for determining COD (chemical oxygen demand) in water by virtue of photoelectrocatalysis method based on visible light response type bismuth vanadate coated electrode |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173165C (en) * | 2002-11-22 | 2004-10-27 | 华东师范大学 | Method for determining COD of water body by using nano titanium dioxide powder |
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2005
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2006279258B2 (en) * | 2005-08-11 | 2009-11-26 | Aqua Diagnostic Pty. Ltd. | Water analysis using a photoelectrochemical method |
| AU2006279258C1 (en) * | 2005-08-11 | 2010-07-08 | Aqua Diagnostic Pty. Ltd. | Water analysis using a photoelectrochemical method |
| WO2007016740A1 (en) * | 2005-08-11 | 2007-02-15 | Aqua Diagnostic Pty. Ltd. | Water analysis using a photoelectrochemical method |
| CN100429500C (en) * | 2006-06-13 | 2008-10-29 | 山东海信环保有限公司 | Method for detecting chemical oxygen demand of water body |
| CN100404123C (en) * | 2006-08-01 | 2008-07-23 | 华东师范大学 | Capillary tube array photo catalysis reactor and its preparation and application |
| CN101105472B (en) * | 2007-06-11 | 2010-05-19 | 大连理工大学 | Water body chemical oxygen demand electrochemical measuring method |
| CN101221146B (en) * | 2008-01-31 | 2010-10-27 | 上海交通大学 | Method for measuring chemical oxygen demand by TiO2 nano hole array electrode photoelectrocatalysis |
| CN102706945B (en) * | 2011-03-28 | 2014-05-21 | 同济大学 | Method for determining waster water COD by simulating sunlight photoelectrocatalysis |
| CN102706945A (en) * | 2011-03-28 | 2012-10-03 | 同济大学 | Method for determining waster water COD by simulating sunlight photoelectrocatalysis |
| CN102866186A (en) * | 2012-09-12 | 2013-01-09 | 合肥工业大学 | Circulating-type water chemical oxygen demand detection photoelectrochemical sensor |
| CN103604847A (en) * | 2013-12-06 | 2014-02-26 | 中国科学技术大学 | Photocoupling method for determining chemical oxygen demand in water body |
| CN103604847B (en) * | 2013-12-06 | 2016-03-09 | 中国科学技术大学 | A kind of photoelectric coupling method for measuring chemical oxygen demand (COD) in water body |
| CN104316581A (en) * | 2014-10-23 | 2015-01-28 | 华南理工大学 | Visible light photoelectrocatalysis based COD (chemical oxygen demand) sensor and preparation method and application thereof |
| CN105510423A (en) * | 2015-12-29 | 2016-04-20 | 南京洁态环保科技有限公司 | Automatic on-line monitor for measuring water body COD (chemical oxygen demand) |
| CN106596838A (en) * | 2016-11-23 | 2017-04-26 | 深圳市朗石科学仪器有限公司 | COD measuring method |
| CN107941731A (en) * | 2017-12-05 | 2018-04-20 | 海南聚能科技创新研究院有限公司 | COD on-line detector in a kind of water quality |
| CN110596208A (en) * | 2019-09-04 | 2019-12-20 | 东华大学 | Method for determining COD (chemical oxygen demand) in water by virtue of photoelectrocatalysis method based on visible light response type bismuth vanadate coated electrode |
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| CN100368799C (en) | 2008-02-13 |
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