CN102659224A - Preparation method and application of nano coated electrode - Google Patents
Preparation method and application of nano coated electrode Download PDFInfo
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- CN102659224A CN102659224A CN2012101724586A CN201210172458A CN102659224A CN 102659224 A CN102659224 A CN 102659224A CN 2012101724586 A CN2012101724586 A CN 2012101724586A CN 201210172458 A CN201210172458 A CN 201210172458A CN 102659224 A CN102659224 A CN 102659224A
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Abstract
The invention discloses a preparation method of a nano coated Ti/SnO2-Sn-Ce electrode and a process and a method for utilizing the same for degradation of perfluorooctane sulfonate in water, and belongs to the technical field of electrochemistry. Perfluorooctane-sulfonate-containing waste water is subjected to electrolytic oxidation by utilizing the nano coated Ti/SnO2-Sn-Ce electrode as an anode and Ti or 304 stainless steel as a cathode. The preparation method is characterized in that perfluorooctane sulfonate can be subjected to fast degradation under mild conditions. By means of electrochemical oxidation, the preparation method is simple in process procedures, convenient to operate, mild in reaction conditions, excellent, stable and reliable in treatment effect and easy to realize industrial application. The nano coated Ti/SnO2-Sn-Ce electrode has the advantages of high oxidation performance, long service life, easiness in processing, low cost and the like.
Description
Technical field
The present invention relates to a kind of nano coating Ti/SnO that uses
2The technology of-Sb-Ce electrode degrading PFOS is used for eliminating the PFOS of waste water, belongs to electrochemistry and environmental technology field.
Background technology
PFOS (PFOS, C
8F
17SO
3H) as tensio-active agent, stain control agent, additive, fire foam, macromolecule emulsifier and agrochemical, its production and use are above 50 years.Because the C-F key has high bond energy (116Kcal/mol), high reduction potential (E among the PFOS
0=3.6V) and low-pole
PFOS possesses extremely strong stability.PFOS is as one of perfluorochemical (PFCs) main home to return in environment; Its stable chemical property, not volatile and can not it extensively is present in natural water, settling, animal and the human body by the characteristic of ecosystem degraded, ecotope and HUMAN HEALTH in serious threat.In recent years, various countries' scholar's research finds that PFOS is in the high density level in the higher animal body, and it is accumulated level and is higher than hundreds of times to thousands of times of persistence organic pollutants such as dense medicine of known organochlorine and dioxin.Relevant research shows that PFOS has multiple toxicity such as hepatotoxicity, genetoxic, genotoxicity, neurotoxicity, development toxicity and internal secretion interference; Can influence metabolism of fat; Influence offspring's male and female and when postpone growing of young animal etc., be considered to one type and have the dirty toxic environmental pollutant of the many devices of whole body.
At present; Global PFOS pollutes and health effects has been caused showing great attention to of national governments and scientific circles; In December, 2002, in the 34th the chemical council joint meeting that OECD holds PFOS is defined as " be present in environment lastingly, have biological savings property and to the deleterious material of the mankind "; On December 30th, 2009, USEPA has issued first " chemical action plan ", and the health and the environmental problem that will cause the long-chain perfluorochemical that comprises PFOS are handled; In addition, European Union on December 27th, 2006 unite in European Parliament and council of ministers and issued " about the restriction PFOS sell and the finger that uses with ".In May, 2009, PFOS and basic salt are formally increased formula together with its precursor perfluoro capryl acyl fluorides to add the accessories B of " Convention of Stockholm " restricted, are intended to limit mondial production and use.
At present, the world wide class is difficult to find out the technology of under mild conditions, effectively degrading and being applicable to large-scale application.Certainly exist to PFOS degradation technique in the water body, comprise ultraviolet photolysis, homogeneous phase photochemical catalysis, ultrasonic radiation, plasma oxidation, the reduction of subcritical attitude Zero-valent Iron and the B that supports one's family
12Reduction etc., though can both obtain certain effect, all existence condition harshness, energy consumption reach defectives such as inapplicable WWT greatly.Therefore, be necessary very much to develop the new technology that can be under gentleness can effectively degrade to PFOS that makes new advances, to use the risk that it brings.
Current; Existing relevant domestic patent to Perfluorocaprylic Acid degradation technique in the water body is put down in writing only 1; Number of patent application is 200510011126.X (Granted publication CN 100347137C); Name is called the method for " a kind of complete
fluorine substitution compound defluorinating and degrading complete ", disclose a kind of under 185nm and 172nm ultraviolet condition the degradation method of photodissociation and photocatalytic degradation Perfluorocaprylic Acid or perfluoro octane sulfonate.
So far, still there is not employing electrochemistry is carried out efficient mineralising purification techniques to PFOS in the water report.
Summary of the invention
The object of the invention is PFOS in the degrading waste water, to the deficiency of prior art, provide a kind of can be under mild conditions to water in the PFOS new type purification technology of effectively degrading.
The objective of the invention is to realize through following technical scheme:
A kind of nano coating Ti/SnO
2The preparation method of-Sn-Ce electrode comprises step:
1. Ti substrate pretreated: at first be that the Ti matrix is polished with sand paper, remove oxide on surface, immerse then in the sodium hydroxide solution, to remove the greasy dirt on surface, etching in oxalic acid solution afterwards is to obtain the grey even curface;
2. tin antimony cerium polymerization forerunner colloidal sol preparation: at first at a certain temperature Hydrocerol A is dissolved in terepthaloyl moietie and obtains Hydrocerol A fat; The salt that adds stanniferous antimony cerium then successively; Remove moisture afterwards at a certain temperature, promptly obtain the polymeric precursor colloidal sol of stanniferous antimony behind the naturally cooling;
3. nano coating Ti/SnO
2-Sb-Ce electrode preparation: adopt and draw formulation that the polymeric precursor colloidal sol of the stanniferous antimony of preparation is overlayed on the Ti matrix; In baking oven, make colloidal sol transfer gel to then; Change roasting in the retort furnace afterwards over to; Repeat preceding process again after taking out the naturally cooling cleaning, drying, repeat certain number of times repeatedly, promptly make nano coating Ti/SnO
2-Sb-Ce electrode.
PFOS in the electrochemical oxidation degradation water:
With 1.0～5.0g/L sodium perchlorate is the solution that the supporting electrolyte preparation contains 5～500mg/L PFOS; With nano coating Ti/SnO
2-Sb-Ce electrode is an anode, is negative electrode with Ti or 304 stainless steels, and the employing flat bed is an electrochemical reactor; The adjusting current density is 2～40mA/cm
2, polar plate spacing is under 2mm～20mm condition the PFOS aqueous solution to be carried out electrochemical oxidation to handle.
Through experiment, in more excellent condition: current density is 10～20mA/cm
2, polar plate spacing is 2mm～5mm, the electrochemical oxidation degraded contains PFOS (100mg/L) waste water, but reaches more than 85% within a short period of time.
Technical scheme by the invention described above provides can be found out; The technology and the method for PFOS degraded in the water provided by the invention, owing to adopt electrochemical oxidation process, it is simple to have a technical process; Easy to operate; Reaction conditions is gentle, and treatment effect is good and reliable and stable, is easy to realize industrial applications.The nano coating Ti/SnO that is adopted
2-Sb-Ce electrode has that oxidation capacity is strong, work-ing life is strong, be easy to advantages such as processing and cheapness.
Description of drawings
Fig. 1 is nano coating Ti/SnO
2-Sb electrode surface pattern.
Fig. 2 is degrading perfluorinated perfluoroetane sulfonic acid effect of electrochemical oxidation and treatment time graph of a relation.
Embodiment
To combine accompanying drawing that the embodiment of the invention is done to describe in detail further below.
The method of PFOS in the efficient mineralized water of a kind of electrochemical oxidation of the present invention, its preferable embodiment comprises step:
Nano coating Ti/SnO
2-Sb electrode preparation:
1. at first with 300 order sand paper to the capable polishing of Ti matrix, immerse 1～2h in 100 ℃ 5% the sodium hydroxide solution then, take out with zero(ppm) water and clean, afterwards etching 2～3h in 100 ℃ of oxalic acid solutions of 10%;
2. under 60 ℃ of temperature, a certain amount of Hydrocerol A is dissolved in the terepthaloyl moietie, dissolving back steady temperature 30～60min is heated to 90 ℃ then fully, adds SnCl
45H
2O, SbCl
3And CeCl
4, fully stir until accomplishing dissolving, be warming up to 100 ℃ and constant temperature 1～3h afterwards, promptly obtain the polymeric precursor colloidal sol of stanniferous antimony cerium behind the naturally cooling, wherein terepthaloyl moietie: Hydrocerol A: SnCl
45H
2O: SbCl
3: CeCl
4(mol ratio) is 100: 30: 8: 1: 2;
3. adopt and draw formulation that the polymeric precursor colloidal sol of the stanniferous antimony cerium of preparation is overlayed on the Ti matrix; In 140 ℃ baking oven, keep 10min to make colloidal sol transfer gel to afterwards; Change in 500 ℃ of retort furnaces roasting 20min in air atmosphere then over to, repeat preceding process again, 30 times repeatedly after taking out the naturally cooling cleaning, drying; 2h and annealing naturally promptly make nano coating Ti/SnO during roasting for the last time
2-Sb-Ce electrode;
The nano coating Ti/SnO of preparation
2-Sb-Ce electrode surface pattern is as shown in Figure 1.The electrode surface granular size is about 100 nanometers as can be seen from Figure 1, is nanomorphic and surface compact, increases reactivity point position greatly.
PFOS in the electrochemical oxidation degradation water:
Preparation contains the solution of 1.4g/L sodium perchlorate and 100mg/L PFOS.Get an amount of solution and inject dull and stereotyped electrolyzer, with the nano coating Ti/SnO of preparation
2-Sb-Ce electrode is an anode, is negative electrode with Ti or 304 stainless steels, and two electrode areas are 60cm
2Regulate polar plate spacing to being fit to size, power-on is also regulated electric current to keep outward current density is 10mA/cm
2, carrying out electrolysis treatment 180min under the room temperature, 15～30min carries out sampling analysis at interval.
Fig. 2 for the present invention to PFOS degradation effect and treatment time relation, can know that by Fig. 2 between 2～10mm polar plate spacing, the PFOS clearance can be greater than 85% through 180min processing.When wherein polar plate spacing was 2mm, 5mm and 10mm, the PFOS clearance was respectively 98.3%, 93.5% and 86.4%.
Above-mentioned description to embodiment is can understand and use the present invention for ease of the those of ordinary skill of this technical field.Any those of ordinary skill in the art can make various modifications to present embodiment easily in the technical scope that the present invention discloses, and are applied to other instance to the principle in this explanation and execute and needn't pass through creative work.Therefore, the invention is not restricted to the embodiment here, do not break away from category of the present invention and make improving and revising and all should be encompassed within protection scope of the present invention.
Claims (2)
1. nano coating Ti/SnO
2The preparation method of-Sn-Ce electrode is characterized in that, may further comprise the steps:
The Ti substrate pretreated: at first with 300 order sand paper to the capable polishing of Ti matrix, immerse 1～2h in 100 ℃ 5% the sodium hydroxide solution then, take out with zero(ppm) water and clean, afterwards etching 2～3h in 100 ℃ of oxalic acid solutions of 10%;
The polymerization forerunner colloidal sol preparation of tin antimony cerium: under 60 ℃ of temperature, a certain amount of Hydrocerol A is dissolved in the terepthaloyl moietie, dissolving back steady temperature 30～60min is heated to 90 ℃ then fully, adds SnCl
45H
2O, SbCl
3And CeCl
4, fully stir until dissolving fully, be warming up to 100 ℃ and constant temperature 1～3h afterwards, promptly obtain the polymeric precursor colloidal sol of stanniferous antimony cerium behind the naturally cooling, wherein terepthaloyl moietie: Hydrocerol A: SnCl
45H
2O: SbCl
3: CeCl
4(mol ratio) is 100: 30: 8: 1: 2;
Nano coating Ti/SnO
2-Sb electrode preparation: adopt and draw formulation that the polymeric precursor colloidal sol of the stanniferous antimony cerium of preparation is coated on the Ti matrix; In 140 ℃ baking oven, keep 10min to make colloidal sol transfer gel to afterwards; Change in 500 ℃ of retort furnaces roasting 20min in air atmosphere then over to, repeat preceding process again, 30 times repeatedly after taking out the naturally cooling cleaning, drying; 2h and annealing naturally promptly make nano coating Ti/SnO during roasting for the last time
2-Sb-Ce electrode.
2. the method for PFOS in the electrochemical oxidation degradation water is characterized in that, is supporting electrolyte with 1.0～5.0g/L sodium perchlorate; With nano coating Ti/SnO prepared in the claim 1
2-Sb-Ce electrode is an anode, is negative electrode with Ti or 304 stainless steels, and the employing flat bed is an electrochemical reactor; The adjusting current density is 2～40mA/cm
2, polar plate spacing is under 2mm～20mm condition the PFOS aqueous solution to be carried out electrochemical oxidation to handle.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614712A (en) * | 2013-12-04 | 2014-03-05 | 淮南师范学院 | Method for preparing Sb and Ce co-doped SnO2 middle layer by sol-gel method |
| CN104016449A (en) * | 2014-05-29 | 2014-09-03 | 北京工业大学 | Preparation and application of Sb-Ni-Nd co-doping SnO2 high catalytic activity positive electrode |
| CN104528887A (en) * | 2014-11-03 | 2015-04-22 | 北京师范大学 | Preparation method of Ti/SnO2-Sb thin film electrode for sewage deep treatment |
| CN104561966A (en) * | 2015-01-30 | 2015-04-29 | 南京大学连云港高新技术研究院 | Preparation method of three-dimensional electrocatalytic composite electrode plate |
| CN104900944A (en) * | 2015-04-17 | 2015-09-09 | 北京师范大学 | photoelectrochemical solar cell based on three-dimensional nanometer silver oxide electrode |
| CN105084467A (en) * | 2014-05-05 | 2015-11-25 | 潘映昆 | Processing reactor of printing and dyeing waste water with catalytic electrode |
| CN108046380A (en) * | 2017-12-13 | 2018-05-18 | 东华大学 | A kind of titanium-based Sn-Sb-Ce oxide electrodes and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4028215A (en) * | 1975-12-29 | 1977-06-07 | Diamond Shamrock Corporation | Manganese dioxide electrode |
| CN1896320A (en) * | 2006-06-19 | 2007-01-17 | 哈尔滨工业大学 | Rare-earth doped titanium-base SnO2 electrolytic electrode and its preparation |
| CN101830542B (en) * | 2010-04-27 | 2011-09-14 | 华南师范大学 | Method for electrolyzing orange G by adopting cerium-doped tin antimony oxide coated titanium electrode |
| CN102348646A (en) * | 2009-03-09 | 2012-02-08 | 汉斯格罗股份公司 | Methods for decomposing partially fluorinated and perfluorinated surfactants |
| CN102464382A (en) * | 2010-11-05 | 2012-05-23 | 同济大学 | High oxygen evolution potential and electrode preparation method for treating fluorine containing organic waste water |
-
2012
- 2012-05-30 CN CN2012101724586A patent/CN102659224A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4028215A (en) * | 1975-12-29 | 1977-06-07 | Diamond Shamrock Corporation | Manganese dioxide electrode |
| CN1896320A (en) * | 2006-06-19 | 2007-01-17 | 哈尔滨工业大学 | Rare-earth doped titanium-base SnO2 electrolytic electrode and its preparation |
| CN102348646A (en) * | 2009-03-09 | 2012-02-08 | 汉斯格罗股份公司 | Methods for decomposing partially fluorinated and perfluorinated surfactants |
| CN101830542B (en) * | 2010-04-27 | 2011-09-14 | 华南师范大学 | Method for electrolyzing orange G by adopting cerium-doped tin antimony oxide coated titanium electrode |
| CN102464382A (en) * | 2010-11-05 | 2012-05-23 | 同济大学 | High oxygen evolution potential and electrode preparation method for treating fluorine containing organic waste water |
Non-Patent Citations (4)
| Title |
|---|
| J. BARRY ET AL.: "The Chemistry of Quadrivalent Lanthanoids. Part I. New Preparative Methods for Cerium(IV) Chloride Complexes", 《INORGANICA CHIMICA ACTA》, no. 53, 31 December 1981 (1981-12-31), pages 17 - 18 * |
| 于广谦等: "四氯化铈(Ⅳ)四氢呋喃络合物和环戊二烯基三氯化铈(Ⅳ)的合成", 《科学通报》, no. 10, 31 December 1985 (1985-12-31), pages 753 - 755 * |
| 方战强等: "稀土Ce掺杂Ti/Sb-SnO2电极的电化学性能及应用", 《稀有金属材料与工程》, vol. 40, no. 9, 30 September 2011 (2011-09-30), pages 1638 - 1642 * |
| 郑佳孝: "四氯化铈(Ⅳ)含氮络合物的合成", 《黑龙江大学自然科学学报》, no. 01, 25 March 1985 (1985-03-25), pages 70 - 72 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614712A (en) * | 2013-12-04 | 2014-03-05 | 淮南师范学院 | Method for preparing Sb and Ce co-doped SnO2 middle layer by sol-gel method |
| CN103614712B (en) * | 2013-12-04 | 2016-05-18 | 淮南师范学院 | Sol-gel process is prepared Sb, Ce codope SnO2The method in intermediate layer |
| CN105084467A (en) * | 2014-05-05 | 2015-11-25 | 潘映昆 | Processing reactor of printing and dyeing waste water with catalytic electrode |
| CN104016449A (en) * | 2014-05-29 | 2014-09-03 | 北京工业大学 | Preparation and application of Sb-Ni-Nd co-doping SnO2 high catalytic activity positive electrode |
| CN104016449B (en) * | 2014-05-29 | 2016-03-02 | 北京工业大学 | A kind of Sb-Ni-Nd codoped SnO 2the preparations and applicatio of high catalytic activity anode |
| CN104528887A (en) * | 2014-11-03 | 2015-04-22 | 北京师范大学 | Preparation method of Ti/SnO2-Sb thin film electrode for sewage deep treatment |
| CN104528887B (en) * | 2014-11-03 | 2017-02-15 | 北京师范大学 | Preparation method of Ti/SnO2-Sb thin film electrode for sewage deep treatment |
| CN104561966A (en) * | 2015-01-30 | 2015-04-29 | 南京大学连云港高新技术研究院 | Preparation method of three-dimensional electrocatalytic composite electrode plate |
| CN104900944A (en) * | 2015-04-17 | 2015-09-09 | 北京师范大学 | photoelectrochemical solar cell based on three-dimensional nanometer silver oxide electrode |
| CN104900944B (en) * | 2015-04-17 | 2017-06-30 | 北京师范大学 | A kind of Photoelectrochemistry based on three-dimensional manometer silver oxide electrode |
| CN108046380A (en) * | 2017-12-13 | 2018-05-18 | 东华大学 | A kind of titanium-based Sn-Sb-Ce oxide electrodes and its preparation method and application |
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Application publication date: 20120912 |