CN105502595A - Titanium-based positive electrode with high oxygen evolution overpotential and preparing method thereof - Google Patents

Titanium-based positive electrode with high oxygen evolution overpotential and preparing method thereof Download PDF

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Publication number
CN105502595A
CN105502595A CN201610092830.0A CN201610092830A CN105502595A CN 105502595 A CN105502595 A CN 105502595A CN 201610092830 A CN201610092830 A CN 201610092830A CN 105502595 A CN105502595 A CN 105502595A
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China
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positive electrode
titanium
titanium base
high oxygen
oxygen separated
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CN201610092830.0A
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周检
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds

Abstract

The invention discloses a titanium-based positive electrode with a high oxygen evolution overpotential and a preparing method thereof. A Cu-doped SnO2 film layer and a titanium substrate are arranged in the electrode from outside to inside. According to the preparing method, the titanium substrate which is subjected to decontamination and TiO2 removal treatment and is in any geometrical shape is coated with a precursor solution containing Sn and Cu, and high-temperature annealing is carried out to form the titanium-based Cu-doped SnO2 positive electrode. By means of Cu element doping, physical and chemical properties of a SnO2 film are changed, and the high oxygen evolution potential of the positive electrode exceeds 2.6 V (vs NHE).

Description

A kind of titanium base positive electrode with high oxygen separated overpotential and preparation method thereof
Technical field
The invention belongs to the positive electrode field of electrochemicial oxidation trade effluent, relate to a kind of titanium base positive electrode with high oxygen separated overpotential and preparation method thereof.
Background technology
Along with China's rapid development of economy, industrial organic waste water pollution problem is day by day serious, directly threatens the healthy of our people, especially the toxic organics contained in water, as phenols, benzene class, polycyclic aromatic hydrocarbons etc., all have carcinogenic, the organism of teratogensis.Electrochemical catalytic oxidation process organic waste water because of can effectively degrading high concentration, microorganism difficult degradation toxic organics and do not produce secondary pollution and be considered to the most promising organic wastewater treatment process of future generation.The kind of positive electrode determines electrochemical catalytic oxidation process organic waste water technique, comprises the formation etc. of organic degradation efficiency and organism by product.At present, most oxidation positive electrode material is all metal oxide.The overpotential for oxygen evolution of these metal oxides is very low.Low overpotential for oxygen evolution is unfavorable for drawing up and analyses the generation of oxygen side reaction, limits the organic kind of electrochemical process oxidative degradation, is unfavorable for electrochemical catalytic oxidation process organic waste water industrial expansion.
Summary of the invention
The object of the invention is overpotential for oxygen evolution this problem low for the existing positive electrode for electrochemical catalytic oxidation, a kind of titanium base positive electrode with high oxygen separated overpotential and preparation method thereof is provided.This electrode is on Titanium base, deposit one deck Cu doping SnO 2film and the positive electrode prepared.By to SnO 2positive electrode carry out Cu element doping, to SnO 2physicochemical property improvement is modified, thus obtains the positive electrode with high oxygen separated overpotential.
The titanium base positive electrode that the present invention has high oxygen separated overpotential is Cu doping SnO from outside to inside respectively 2layer and Titanium base.
Described Titanium base is the titanium metal of all specifications, as titanium foil, titanium plate, titanium net and titanium alloy etc.;
Described Titanium base can be random geometry, as square, and cylinder shape etc.;
Described Cu doping SnO 2film is pantomorphic film, as non-crystalline state, polycrystalline state, monocrystalline state etc.;
Described Cu doping SnO 2the thickness of film is more than 1 μm;
Described Cu doping SnO 2the Cu doping content (atomic ratio of Cu and Sn) in 1% to 30% scope of film.
Another object of the present invention is to provide the above-mentioned preparation method with the titanium base positive electrode of high oxygen separated overpotential, and the method comprises the following steps: to be adulterated SnO as Cu by Titanium base 2the propping material of film; The organic pollutants such as the oil stain on Titanium base surface and titanium dioxide film are removed; Preparation is containing the precursor solution of Sn, Cu; Titanium base surface will be coated in containing Sn, Cu precursor solution; Thermosetting titanium base Cu is added to the Titanium base scribbling precursor solution and mixes SnO 2positive electrode.
The removal of described Titanium base surface organic matter, adopts organic solvent or alkali lye to remove, as alcohol, and NaOH etc.;
The removal of described Titanium base superficial silicon dioxide titanium film, adopts acid to remove Titanium base corrosion, example hydrochloric acid, oxalic acid etc.;
The described preparation containing Sn, Cu precursor liquid is dissolved in containing Sn, Cu compound in solvent.Solvent can be water, organic solvent, all solvable solution containing Sn, Cu compound such as acid;
Described Sn, Cu precursor solution coating can be all coated techniques such as dip coating, brushing, spray application;
Described Titanium base heating is placed on the heating by Titanium base, and this heating unit can be hot plate, muffle furnace etc.;
Described Titanium base Heating temperature within the scope of 350-700 DEG C, preferably 550 DEG C.
The invention has the beneficial effects as follows: the invention provides a kind of titanium base positive electrode with high oxygen separated overpotential and preparation method thereof, utilize Cu doped element to SnO 2the physicochemical property of film improve, and improve the overpotential for oxygen evolution of titanium base positive electrode to a great extent, can realize the positive electrode of overpotential for oxygen evolution more than 2.6V (vsNHE).
Accompanying drawing explanation
Fig. 1 is the structural representation that the present invention has the titanium base positive electrode of high oxygen separated overpotential, and wherein 1 is Cu doping SnO 2film, 2 is Titanium base;
Fig. 2 is titanium base Cu of the present invention doping SnO 2the scanning electron microscopic picture of positive electrode;
Fig. 3 is titanium base Cu of the present invention doping SnO 2the cyclic voltammetry curve figure of the sign overpotential for oxygen evolution of positive electrode.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, gives detailed embodiment and specific operation process, but protection scope of the present invention is not limited to following embodiment.
The titanium base positive electrode with high oxygen separated overpotential disclosed in this invention.Electrode is Cu doping SnO from outside to inside respectively 2layer and Titanium base.
Embodiment 1:
The present embodiment comprises the following steps:
Step (1), as shown in Figure 1, selection thickness is 0.5mm, and area is 9cm 2titanium plate as Titanium base, carry out making herbs into wool process by blasting craft to titanium plate surface, the size of the grains of sand is 300 orders.Adopt the titanium plate after sandblasting to put in spirituous solution and carry out ultrasonic cleaning 10 minutes, then by the titanium plate after cleaning with 10% oxalic acid corrode 30 minutes, the titanium plate deionized water rinsing will corroded afterwards, finally utilizes nitrogen to be dried up by titanium plate.
The SnCl of step (2), weighing 8.0g 45H 2o also puts it in the alcohol of 50mL, utilizes magnetic stirring apparatus to carry out fully stirring obtaining limpid homogeneous solution.
The CuNO of step (3), weighing 0.20g 3and put it in the solution that step 2 obtains, utilize magnetic stirring apparatus to carry out fully stirring obtaining limpid homogeneous solution.
Step (4), titanium plate step 1 obtained are placed and are heated on hot plate, until the temperature of titanium plate is 550 DEG C.
Step (5), measure appropriate precursor solution and put in spraying gun, air compressor is utilized to provide air gas, enter into spraying gun with the flow of 100L/H precursor aqueous solution droplet is carried out, spraying to the temperature that step 4 obtains is on the titanium plate of 550 DEG C, height between shower nozzle and titanium plate is 2cm, continues spraying until obtain the even Cu doping SnO of desired thickness 2film, finally obtains titanium base Cu doping SnO 2positive electrode, its surface topography as shown in Figure 2.
Step (6), utilize electrochemical workstation, adopt cyclic voltammetry to adulterate SnO to titanium base Cu 2positive electrode carries out overpotential for oxygen evolution to be tested, and test condition is: voltage scan rate is 100mV/s, and solution is the H of 0.5M 2sO 4, titanium base Cu adulterates SnO 2the area of positive electrode is 1cm 2, area is 1cm 2pt electrode be to electrode, saturated calomel electrode is reference electrode, institute the cyclic voltammetry curve that obtains as shown in Figure 3.
Embodiment 2:
The present embodiment comprises the following steps:
Step (1), as shown in Figure 1, selection thickness is 0.5mm, and area is 9cm 2titanium net as Titanium base, carry out making herbs into wool process by blasting craft to titanium plate surface, the size of the grains of sand is 300 orders.Titanium plate after sandblasting is put in spirituous solution and carries out ultrasonic cleaning 10 minutes, then by the titanium net after cleaning with 18% hcl corrosion 30 minutes, the titanium net deionized water rinsing will corroded afterwards, finally utilizes nitrogen to be dried up by titanium plate.
The SnCl of step (2), weighing 8.0g 45H 2o, and put it in the alcohol of 50mL, utilize magnetic stirring apparatus to carry out fully stirring obtaining limpid homogeneous solution.
The CuNO of step (3), weighing 0.1g 3and put it in the solution that step 2 obtains, utilize magnetic stirring apparatus to carry out fully stirring obtaining limpid homogeneous solution.
Step (4), titanium net step 1 obtained are put in the precursor aqueous solution that step 2 and step 3 obtain, and flood 2 minutes, take out the loft drier inner drying 10 minutes putting into 100 DEG C.
Temperature put into by step (5), titanium net step 4 obtained is carry out annealing in the muffle furnace of 550 DEG C 10 minutes, obtains Cu doping SnO 2film.
Step (6), the titanium net repeating step 1-5 will obtained after annealing, the SnO until Cu adulterates 2till the thickness of film is enough thick, finally obtains titanium base Cu and to adulterate SnO 2positive electrode.
Embodiment 3:
The present embodiment comprises the following steps:
Step (1), as shown in Figure 1, selection thickness is 1mm, area be 9cm2 titanium plate as Titanium base, carry out making herbs into wool process by blasting craft to titanium plate surface, the size of the grains of sand is 300 orders.Adopt the titanium plate after sandblasting to put in spirituous solution and carry out ultrasonic cleaning 10 minutes, then by the titanium plate after cleaning with 10% oxalic acid corrode 30 minutes, the titanium plate deionized water rinsing will corroded afterwards, finally utilizes nitrogen to be dried up by titanium plate.
The SnCl of step (2), weighing 7.0g 22H 2o also puts it in the alcohol of 50mL, utilizes magnetic stirring apparatus to carry out fully stirring obtaining limpid homogeneous solution.
The CuNO of step (3), weighing 0.08g 3and put it in the solution that step 2 obtains, utilize magnetic stirring apparatus to carry out fully stirring obtaining limpid homogeneous solution.
Step (4), to pick the precursor aqueous solution that step 3 obtains with hairbrush, then precursor aqueous solution is brushed on the uniform titanium plate surface obtained in step 1, puts into the loft drier inner drying 10 minutes of 100 DEG C afterwards.
Temperature put into by step (5), titanium plate step 4 obtained is carry out annealing in the muffle furnace of 550 DEG C 10 minutes, forms Cu doping SnO on titanium plate surface 2film.
Step (6), the titanium plate repeating step 1-5 will obtained after annealing, the SnO until Cu adulterates 2till the thickness of film is enough thick, finally obtains titanium base Cu and to adulterate SnO 2positive electrode.
The content be not described in detail in specification sheets of the present invention belongs to the known prior art of professional and technical personnel in the field.Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet application claims, all belongs to protection scope of the present invention.

Claims (8)

1. there is a titanium base positive electrode for high oxygen separated overpotential, it is characterized in that on Titanium base, deposit one deck Cu doping SnO 2film; Described titanium base positive electrode is Cu doping SnO from outside to inside respectively 2layer and Titanium base.
2. there is a preparation method for the titanium base positive electrode of high oxygen separated overpotential, it is characterized in that the method is as follows: Titanium base to be adulterated SnO as Cu 2the propping material of film; The organic pollutants such as the oil stain on Titanium base surface and titanium dioxide film are removed; Preparation is containing the precursor solution of Sn, Cu; Titanium base surface will be coated in containing Sn, Cu precursor solution; Thermosetting titanium base Cu is added to the Titanium base scribbling precursor solution and mixes SnO 2positive electrode.
3. as claimed in claim 1 a kind of there is high oxygen separated overpotential titanium base positive electrode or a kind of preparation method with the titanium base positive electrode of high oxygen separated overpotential as claimed in claim 2, it is characterized in that Titanium base is the titanium metal of any specification, as titanium foil, titanium plate, titanium net and titanium alloy etc.
4. as claimed in claim 1 a kind of there is high oxygen separated overpotential titanium base positive electrode or a kind of preparation method with the titanium base positive electrode of high oxygen separated overpotential as claimed in claim 2, it is characterized in that Titanium base can be random geometry.
5. as claimed in claim 1 a kind of there is high oxygen separated overpotential titanium base positive electrode or a kind of preparation method with the titanium base positive electrode of high oxygen separated overpotential as claimed in claim 2, it is characterized in that Titanium base Heating temperature is within the scope of 350-700 DEG C, preferably 550 DEG C.
6. as claimed in claim 1 a kind of there is high oxygen separated overpotential titanium base positive electrode or a kind of preparation method with the titanium base positive electrode of high oxygen separated overpotential as claimed in claim 2, it is characterized in that Cu adulterates SnO 2film is pantomorphic film.
7. as claimed in claim 1 a kind of there is high oxygen separated overpotential titanium base positive electrode or a kind of preparation method with the titanium base positive electrode of high oxygen separated overpotential as claimed in claim 2, it is characterized in that Cu adulterates SnO 2the thickness of film is more than 1 μm.
8. as claimed in claim 1 a kind of there is high oxygen separated overpotential titanium base positive electrode or a kind of preparation method with the titanium base positive electrode of high oxygen separated overpotential as claimed in claim 2, it is characterized in that Cu adulterates SnO 2the Cu doping content (atomic ratio of Cu and Sn) in 1% to 30% scope of film.
CN201610092830.0A 2016-02-19 2016-02-19 Titanium-based positive electrode with high oxygen evolution overpotential and preparing method thereof Pending CN105502595A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109824126A (en) * 2019-03-29 2019-05-31 杭州睿清环保科技有限公司 A kind of tin oxide positive electrode and preparation method with oxygen evolution potential
CN110655150A (en) * 2018-06-28 2020-01-07 杭州睿清环保科技有限公司 Novel titanium-based tin oxide anode and preparation method thereof
CN113697908A (en) * 2021-09-13 2021-11-26 东莞理工学院 Preparation method of electrode for electrocatalytic degradation of printing and dyeing wastewater

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000233186A (en) * 1999-02-10 2000-08-29 Ebara Corp Hydrothermal electrolysis apparatus
CN101905912A (en) * 2010-07-08 2010-12-08 中国船舶重工集团公司第七二五研究所 Method for preparing organic pollutant-degrading electrode material
CN102689948A (en) * 2011-03-24 2012-09-26 同济大学 SnO2 electrode for treating fluorine-containing organic pollutants
CN104876305A (en) * 2015-05-21 2015-09-02 上海大学 Preparation method of copper-doped coated electrode for treating printing and dyeing wastewater

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000233186A (en) * 1999-02-10 2000-08-29 Ebara Corp Hydrothermal electrolysis apparatus
CN101905912A (en) * 2010-07-08 2010-12-08 中国船舶重工集团公司第七二五研究所 Method for preparing organic pollutant-degrading electrode material
CN102689948A (en) * 2011-03-24 2012-09-26 同济大学 SnO2 electrode for treating fluorine-containing organic pollutants
CN104876305A (en) * 2015-05-21 2015-09-02 上海大学 Preparation method of copper-doped coated electrode for treating printing and dyeing wastewater

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110655150A (en) * 2018-06-28 2020-01-07 杭州睿清环保科技有限公司 Novel titanium-based tin oxide anode and preparation method thereof
CN110655150B (en) * 2018-06-28 2023-10-31 杭州睿清环保科技有限公司 Titanium-based tin oxide anode electrode and preparation method thereof
CN109824126A (en) * 2019-03-29 2019-05-31 杭州睿清环保科技有限公司 A kind of tin oxide positive electrode and preparation method with oxygen evolution potential
CN109824126B (en) * 2019-03-29 2022-06-10 杭州睿清环保科技有限公司 Tin oxide anode electrode with high oxygen evolution potential and preparation method
CN113697908A (en) * 2021-09-13 2021-11-26 东莞理工学院 Preparation method of electrode for electrocatalytic degradation of printing and dyeing wastewater

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