CN101349017A - Method for reducing sulfur dyes by electrocatalysis - Google Patents
Method for reducing sulfur dyes by electrocatalysis Download PDFInfo
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Abstract
The invention provides a method for reducing a sulfur dye by the electrocatalysis, comprising the following steps that: a silver electrode is taken as a cathode, an inert electrode is taken as an anode, the sulfur dye is added into a cathode electrolyzing solution, the electrolysis is performed at a temperature of between 5 and 80 DEG C on the condition that the initial concentration of the sulfur dye in the cathode electrolyzing solution is between 1 and 500g/L, and the sulfur dye is reduced to the water-soluble state. The method has the advantages that the chemical medicine is small in dosage, the high current density electrolysis is realized, the current efficiency is high; according to the method, the sulfur dye is reduced to the soluble state and is dyed, and the no waste water is discharged basically.
Description
(1) technical field
The present invention relates to a kind of method of reducing sulfur dyes by electrocatalysis, being specially a kind of is the method that negative electrode reduces to SULPHUR DYES with the silver electrode.
(2) background technology
SULPHUR DYES is one of main dyestuff during cellulose dyeing is used.Its advantage is that production technology is brief, cheap, light fastness is good, applicability is strong.In 1992 to 2002 10 years, the year consumption that is used for the SULPHUR DYES of cellulose fibre printing and dyeing on the world market is about about 70,000 tons.SULPHUR DYES does not contain azo group, heavy metal and adsorbable organohalogen compounds, generally neither anaphylaxis dyestuff and carcinogenic dyestuff, be considered to a kind of non-toxic dye.Yet the reductant when 90% SULPHUR DYES is used in the world at present is still vulcanized sodium, and all is excessive.Therefore, in the sulfur dyeing process, can produce the dyeing waste water that contains high concentration sulfide in a large number.If the sulphide-containing waste water of such high concentration is directly discharged, can cause serious environmental to pollute.
The method that has for this reason occurred the electrochemical reduction SULPHUR DYES at present, promptly replace reductant that reducing dyes is become water-soluble attitude by electric energy, dye according to traditional step then, so can significantly reduce the discharging of the consumption and the waste water of reductant, the overall manufacturing cost is reduced.
Current density is low, the complicated shortcoming that maybe need use the redox medium of cell construction but the method for the present electrochemical reduction SULPHUR DYES of utilizing has mostly.Comprising the disclosed Direct Electrochemistry reduction process of utilizing many negative electrodes in J.Appl.Electrochem.28 (1998) 1243, Dyes and Pigments 77 (2008) 502 and the United States Patent (USP) 6312583 etc. is arranged; Disclosed indirect electrochemical reduction process in United States Patent (USP) 5244549 and the Chinese patent 200410056347.4.
(3) summary of the invention
Main purpose of the present invention is to provide a kind of consumption that reduces chemicals that not only can reach; And can realize the electroreduction method of high current density electrolysis, high efficiency SULPHUR DYES.
The technical solution used in the present invention is:
A kind of method of reducing sulfur dyes by electrocatalysis, described method comprises: be that negative electrode, inert electrode are anode with the silver electrode, in catholyte, add SULPHUR DYES, SULPHUR DYES initial concentration 1～500g/L in catholyte (under preferred 50～200g/L) conditions, carry out electrolysis under 5～80 ℃, is reduced to water-soluble attitude with SULPHUR DYES.
Key of the present invention is as negative electrode SULPHUR DYES to be carried out electroreduction with silver electrode, find through experiment: silver has very strong catalytic capability to the electro-reduction reaction of SULPHUR DYES, no matter be the insoluble SULPHUR DYES of oxidation state, or the SULPHUR DYES leucobase of partial reduction can both be realized reduction expeditiously on silver electrode.
Described negative electrode can be the argent of tabular, shaft-like, lead, screen cloth, netted, ulotrichy or sheet form, the screen cloth of preferred development; Negative electrode also can be made up of the silver coating that is coated on the another kind of matrix, and matrix comprises stone mill, stainless steel, metallic nickel and Titanium, carbon, platinum etc.What adopt is diaphragm cell, and available diaphragm material has, the Teflon of various anion and cation-exchange membrane, porous, asbestos and glass.Electrolysis can intermittently be carried out or carry out in continuous or semicontinuous mode.
Anode can be any chemical inert material, comprise: for example metal oxide stainless steel, metallic nickel, platinum, graphite, carbon, brown lead oxide, the silver oxide on silver or the alloy such as HastelloyC, preferred anode material is a stainless steel.Electrode can be the form of tabular, shaft-like, lead, screen cloth, netted, ulotrichy or sheet, the screen cloth of preferred development.Anode also can be made up of the coating that is coated on the another kind of material, and one of them example is that the metal oxide containing precious metals such as ruthenium-oxide is applied on the titanium.
The solvent of described catholyte is the mixture of water or water and organic solvent, and described organic solvent is alcohol, oxolane, dimethyl formamide or the dimethylacetylamide of C1～C6; The electrolyte of described catholyte is alkali metal hydroxide, quaternary ammonium salt, alkali chloride or carbonate, and the electrolyte mass concentration is 0.4～40% (being preferably 4～20%) in the catholyte.NaOH is most preferred supporting electrolyte.
The kind of anodolyte and concentration are not The key factor.Preferably, the solvent of described anolyte is the mixture of water or water and organic solvent, and described organic solvent is alcohol, oxolane, dimethyl formamide or the dimethylacetylamide of C1～C6; The electrolyte of described catholyte is alkali metal hydroxide, quaternary ammonium salt, alkali chloride or carbonate, and the electrolyte mass concentration is 0.4～40% in the catholyte.
The state of disturbance of the shape of electrolytic cell, internal structure and solution is not a The key factor.The proper temperature that is used for the SULPHUR DYES reduction is 5～80 ℃, and preferred temperature is 20～60 ℃, and Optimal Temperature is 20～40 ℃.Preferably, described electrolysis is carried out under 20～60 ℃, and current density is 0.01～1.00A/cm
2, tank voltage 2.5～5.5V, 2～100 hours conduction time.
Preferably, described silver electrode is an active silver electrode, described active silver electrode prepares (specifically can referring at first to file Chinese patent 200810059789.2) as follows: containing in the anionic aqueous solution, earlier silver electrode is carried out anodic oxidation reactions, made electrode surface form the oxidation state layer of silver, again polarity of electrode is reversed, silver electrode is carried out cathodic reduction reaction, obtain described active silver electrode; Described anion is one or more the combination of halide ion and following anion: 1. perchlorate, 2. hypochlorite ion, 3. hydroxide ion, 4. nitrate ion, 5. sulfate ion, 6. carbanion, 7. organic acid ion, 8. phenolic hydroxyl group radical ion; Anion concentration is 0.01～20mol/L in the described aqueous solution.
Concrete, described active silver electrode is prepared by following method: containing perchlorate 0.5～2mol/L, hydroxide ion 0.5～2mol/L, in the aqueous solution of nitrate ion 0.5～2mol/L, connect power anode with silver electrode, graphite electrode connects power cathode, in 20～60 ℃, under tank voltage 2.5～4.0V condition, silver electrode is carried out anodic oxidation reactions, electrode potential until silver electrode is 0.8～1.0V, again polarity of electrode is reversed, connect power cathode with silver electrode, graphite electrode connects power anode, in 20～60 ℃, under tank voltage 2.5～4.0V condition, silver electrode is carried out cathodic reduction reaction, until the electrode potential of silver electrode be-0.5～-0.8V, repeat described anodic oxidation reactions and cathodic reduction reaction 2～6 times, obtain described active silver electrode.
Beneficial effect of the present invention is mainly reflected in: the chemicals consumption is few, can realize high current density electrolysis, current efficiency height, according to the inventive method SULPHUR DYES is reduced to water-soluble attitude after, dye basic non-wastewater discharge again.
(4) specific embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
In barrier film (Nafion 424) electrolytic cell, expansion screen cloth silver electrode is a negative electrode, and apparent size is 10 * 15 * 0.1cm
2Stainless (steel) wire is an anode, and apparent size is 10 * 15 * 0.1cm
2Catholyte is that the sodium hydroxide solution of 1.0L 4.0wt% adds 100g sulphur black (C.I. SULPHUR BLACK 1 200); Anolyte is the sodium hydrate aqueous solution of 1.0L 4.0wt%.Catholyte and anolyte are played circulation with magnetic drive pump respectively, and flow all is 5.0L/min.The electrolytic cell galvanization is carried out electrolysis, and current density is 0.033A/cm
2, reaction temperature is controlled at 25 ± 2 ℃, and tank voltage is about 2.5～3.5V.Switch on after 10 hours, stop electrolysis.With platinum electrode the electrolyte before and after the electrolysis is carried out potential measurement, current potential respectively 0.25V and-0.53V.Get 10mL used for electrolyte iron hydrofining and carry out titration, the current efficiency that calculates is 68%.
Embodiment 2:
The active silver electrode preparation:
In undivided cell, adopt screen cloth type silver as working electrode, apparent size is 0.1cm * 10cm * 15cm, graphite of the same area is to electrode, two electrodes 2cm of being separated by.Electrolyte is that (CATION is Na to the 1000mL aqueous solution that contains 0.24mol/L fluorine ion and 0.5mol/L sulfate ion
+), it is static that electrolyte keeps.Logical then direct current carries out oxidation to silver electrode, and current density is 50mA/cm
2, treat that electrode potential rises to 1.0V after, the upset polarity silver electrode is reduced, current density is 100mA/cm
2, treat electrode potential drop to-0.8V after, repeat this electrochemical redox process 4 times.Reaction temperature is controlled at 25 ℃, and tank voltage is controlled at 2.5～4.0V.Take out silver electrode, place deionization standby.
In barrier film (Nafion 424) electrolytic cell, be negative electrode with aforementioned screen cloth active silver electrode, apparent size is 10cm * 15cm * 0.1cm; Stainless (steel) wire is an anode, and apparent size is 10cm * 15cm * 0.1cm.Catholyte is that the sodium hydroxide solution of 1.0L 4.0wt% adds 100g sulphur black (C.I. SULPHUR BLACK 1 200); Anolyte is the sodium hydrate aqueous solution of 1.0L 4.0wt%.Anode and cathode liquid is played circulation with magnetic drive pump respectively, and flow all is 5.0L/min.The electrolytic cell galvanization is carried out electrolysis, and current density is 0.033A/cm
2, reaction temperature is controlled at 25 ± 2 ℃, and tank voltage is about 2.5～3.5V.Switch on after 10 hours, stop electrolysis.With platinum electrode the electrolyte before and after the electrolysis is carried out potential measurement, current potential respectively 0.25V and-0.61V.Get 10mL used for electrolyte iron hydrofining and carry out titration, the current efficiency that calculates is 88%.
Embodiment 3:
In barrier film (Nafion 424) electrolytic cell, graphite electrode is a negative electrode, and apparent size is 10cm * 15cm * 0.1cm; Stainless (steel) wire is an anode, and apparent size is 10cm * 15cm * 0.1cm.Catholyte is that the sodium hydroxide solution of 1.0L 4.0wt% adds 100g sulphur black (C.I. SULPHUR BLACK 1 200) and 0.02g silver nitrate (effect of silver nitrate herein is in order to make graphite electrode surface plate silver layer); Anolyte is the sodium hydrate aqueous solution of 1.0L 4.0wt%.Anode and cathode liquid is played circulation with magnetic drive pump respectively, and flow all is 5.0L/min.The electrolytic cell galvanization is carried out electrolysis, and current density is 0.033A/cm
2, reaction temperature is controlled at 25 ± 2 ℃, and tank voltage is about 2.5～3.5V.Switch on after 10 hours, stop electrolysis.With platinum electrode the electrolyte before and after the electrolysis is carried out potential measurement, current potential respectively 0.25V and-0.57V.Get 10mL used for electrolyte iron hydrofining and carry out titration, the current efficiency that calculates is 81%.
Embodiment 4:
In barrier film (Nafion 424) electrolytic cell, stainless (steel) wire is a negative electrode, and apparent size is 10cm * 15cm * 0.1cm; Stainless (steel) wire is an anode, and apparent size is 10cm * 15cm * 0.1cm.Catholyte is that the sodium hydroxide solution of 1.0L 4.0wt% adds 100g sulphur black (C.I. SULPHUR BLACK 1 200) and 0.02g silver nitrate (effect of silver nitrate herein is in order to make the stainless steel electrode surface plate silver layer); Anolyte is the sodium hydrate aqueous solution of 1.0L 4.0wt%.Anode and cathode liquid is played circulation with magnetic drive pump respectively, and flow all is 5.0L/min.The electrolytic cell galvanization is carried out electrolysis, and current density is 0.033A/cm
2, reaction temperature is controlled at 25 ± 2 ℃, and tank voltage is about 2.5～3.5V.Switch on after 10 hours, stop electrolysis.With platinum electrode the electrolyte before and after the electrolysis is carried out potential measurement, current potential respectively 0.25V and-0.53V.Get 10mL used for electrolyte iron hydrofining and carry out titration, the current efficiency that calculates is 65%.
Embodiment 5:
Active silver electrode preparation: in undivided cell, adopt screen cloth type silver as working electrode, apparent size is 0.1cm * 10cm * 15cm, and graphite of the same area is to electrode, two electrodes 2cm of being separated by.Electrolyte is that (CATION is Na to the 1000mL aqueous solution that contains 0.5mol/L perchlorate, 0.5mol/L hydroxide ion and 0.5mol/L nitrate ion
+), it is static that electrolyte keeps.Logical then direct current carries out oxidation to silver electrode, and current density is 50mA/cm
2, treat that electrode potential rises to 1.0V after, the upset polarity silver electrode is reduced, current density is 100mA/cm
2, treat electrode potential drop to-0.8V after, repeat this electrochemical redox process 4 times.Reaction temperature is controlled at 25 ℃, and tank voltage is controlled at 2.5～4.0V.Take out silver electrode, place deionization standby.
In barrier film (Nafion 424) electrolytic cell, aforementioned screen cloth active silver electrode is a negative electrode, and apparent size is 10cm * 15cm * 0.1cm; Stainless (steel) wire is an anode, and apparent size is 10 * 15 * 0.1cm
2Catholyte is that the sodium hydroxide solution of 1.0L 4.0wt% adds 100g sulphur black (C.I. sulfur blue 43) and 1.0 vulcanized sodium; Anolyte is the sodium hydrate aqueous solution of 1.0L 4.0wt%.Anode and cathode liquid is played circulation with magnetic drive pump respectively, and flow all is 5.0L/min.The electrolytic cell galvanization is carried out electrolysis, and current density is 0.033A/cm
2, reaction temperature is controlled at 25 ± 2 ℃, and tank voltage is about 2.5～3.5V.Switch on after 10 hours, stop electrolysis.With platinum electrode the electrolyte before and after the electrolysis is carried out potential measurement, current potential respectively 0.28V and-0.57V.Get 10mL used for electrolyte iron hydrofining and carry out titration, the current efficiency that calculates is 82%.
Embodiment 6:
Active silver electrode preparation: in undivided cell, adopt screen cloth type silver as working electrode, apparent size is 0.1cm * 10cm * 15cm, and graphite of the same area is to electrode, two electrodes 2cm of being separated by.Electrolyte is that (CATION is Na to the 1000mL aqueous solution that contains 0.5mol/L perchlorate, 0.5mol/L hydroxide ion and 0.5mol/L nitrate ion
+), it is static that electrolyte keeps.Logical then direct current carries out oxidation to silver electrode, and current density is 50mA/cm
2, treat that electrode potential rises to 1.0V after, the upset polarity silver electrode is reduced, current density is 100mA/cm
2, treat electrode potential drop to-0.8V after, repeat this electrochemical redox process 4 times.Reaction temperature is controlled at 25 ℃, and tank voltage is controlled at 2.5～4.0V.Take out silver electrode, place deionization standby.
In barrier film (Nafion 424) electrolytic cell, aforementioned screen cloth active silver electrode is a negative electrode, and apparent size is 10cm * 15cm * 0.1cm; Stainless (steel) wire is an anode, and apparent size is 10 * 15 * 0.1cm
2Catholyte is that the sodium hydroxide solution of 1.0L 4.0wt% adds 100g sulphur black (sulfuration black BRRN) and 1.0 vulcanized sodium; Anolyte is the sodium hydrate aqueous solution of 1.0L 4.0wt%.Anode and cathode liquid is played circulation with magnetic drive pump respectively, and flow all is 5.0L/min.The electrolytic cell galvanization is carried out electrolysis, and current density is 0.033A/cm
2, reaction temperature is controlled at 25 ± 2 ℃, and tank voltage is about 2.5～3.5V.Switch on after 10 hours, stop electrolysis.With platinum electrode the electrolyte before and after the electrolysis is carried out potential measurement, current potential respectively 0.28V and-0.58V.Get 10mL used for electrolyte iron hydrofining and carry out titration, the current efficiency that calculates is 88%.
Embodiment 7:
Active silver electrode preparation: in undivided cell, adopt screen cloth type silver as working electrode, apparent size is 0.1cm * 10cm * 15cm, and graphite of the same area is to electrode, two electrodes 2cm of being separated by.Electrolyte is that (CATION is Na to the 1000mL aqueous solution that contains 0.5mol/L perchlorate, 0.5mol/L hydroxide ion and 0.5mol/L nitrate ion
+), it is static that electrolyte keeps.Logical then direct current carries out oxidation to silver electrode, and current density is 50mA/cm
2, treat that electrode potential rises to 1.0V after, the upset polarity silver electrode is reduced, current density is 100mA/cm
2, treat electrode potential drop to-0.8V after, repeat this electrochemical redox process 4 times.Reaction temperature is controlled at 25 ℃, and tank voltage is controlled at 2.5～4.0V.Take out silver electrode, place deionization standby.
In barrier film (Nafion 424) electrolytic cell, aforementioned screen cloth active silver electrode is a negative electrode, and apparent size is 10cm * 15cm * 0.1cm; Stainless (steel) wire is an anode, and apparent size is 10 * 15 * 0.1cm
2Catholyte is that the sodium hydroxide solution of 1.0L 4.0wt% adds 100g sulphur black (sulfur red brown b3r) and 1.0 vulcanized sodium; Anolyte is the sodium hydrate aqueous solution of 1.0L 4.0wt%.Anode and cathode liquid is played circulation with magnetic drive pump respectively, and flow all is 5.0L/min.The electrolytic cell galvanization is carried out electrolysis, and current density is 0.033A/cm
2, reaction temperature is controlled at 25 ± 2 ℃, and tank voltage is about 2.5～3.5V.Switch on after 10 hours, stop electrolysis.With platinum electrode the electrolyte before and after the electrolysis is carried out potential measurement, current potential respectively 0.28V and-0.56V.Get 10mL used for electrolyte iron hydrofining and carry out titration, the current efficiency that calculates is 80%.
Embodiment 8:
Active silver electrode preparation: in undivided cell, adopt screen cloth type silver as working electrode, apparent size is 0.1cm * 10cm * 15cm, and graphite of the same area is to electrode, two electrodes 2cm of being separated by.Electrolyte is that (CATION is Na to the 1000mL aqueous solution that contains 0.5mol/L perchlorate, 0.5mol/L hydroxide ion and 0.5mol/L nitrate ion
+), it is static that electrolyte keeps.Logical then direct current carries out oxidation to silver electrode, and current density is 50mA/cm
2, treat that electrode potential rises to 1.0V after, the upset polarity silver electrode is reduced, current density is 100mA/cm
2, treat electrode potential drop to-0.8V after, repeat this electrochemical redox process 4 times.Reaction temperature is controlled at 25 ℃, and tank voltage is controlled at 2.5～4.0V.Take out silver electrode, place deionization standby.
In barrier film (Nafion 424) electrolytic cell, aforementioned screen cloth active silver electrode is a negative electrode, and apparent size is 10cm * 15cm * 0.1cm; Stainless (steel) wire is an anode, and apparent size is 10 * 15 * 0.1cm
2Catholyte is that the sodium hydroxide solution of 1.0L 4.0wt% adds 100g sulphur black (sulfur yellow 1) and 1.0 vulcanized sodium; Anolyte is the sodium hydrate aqueous solution of 1.0L 4.0wt%.Anode and cathode liquid is played circulation with magnetic drive pump respectively, and flow all is 5.0L/min.The electrolytic cell galvanization is carried out electrolysis, and current density is 0.033A/cm
2, reaction temperature is controlled at 25 ± 2 ℃, and tank voltage is about 2.5～3.5V.Switch on after 10 hours, stop electrolysis.With platinum electrode the electrolyte before and after the electrolysis is carried out potential measurement, current potential respectively 0.28V and-0.55V.Get 10mL used for electrolyte iron hydrofining and carry out titration, the current efficiency that calculates is 75%.
Comparative example 1:
In barrier film (Nafion 424) electrolytic cell, graphite electrode is a negative electrode, and apparent size is 10cm * 15cm * 0.1cm; Stainless (steel) wire is an anode, and apparent size is 10cm * 15cm * 0.1cm.Catholyte is that the sodium hydroxide solution of 1.0L 4.0wt% adds 100g sulphur black (C.I. SULPHUR BLACK 1 200); Anolyte is the sodium hydrate aqueous solution of 1.0L 4.0wt%.Anode and cathode liquid is played circulation with magnetic drive pump respectively, and flow all is 5.0L/min.The electrolytic cell galvanization is carried out electrolysis, and current density is 0.033A/cm
2, reaction temperature is controlled at 25 ± 2 ℃, and tank voltage is about 2.5～3.5V.Switch on after 10 hours, stop electrolysis.With platinum electrode the electrolyte before and after the electrolysis is carried out potential measurement, current potential respectively 0.25V and-0.52V.Get 10mL used for electrolyte iron hydrofining and carry out titration, the current efficiency that calculates is 41%.
Comparative example 2:
In barrier film (Nafion 424) electrolytic cell, stainless (steel) wire is a negative electrode, and apparent size is 10cm * 15cm * 0.1cm; Stainless (steel) wire is an anode, and apparent size is 10cm * 15cm * 0.1cm.Catholyte is that the sodium hydroxide solution of 1.0L 4.0wt% adds 100g sulphur black (C.I. SULPHUR BLACK 1 200); Anolyte is the sodium hydrate aqueous solution of 1.0L 4.0wt%.Anode and cathode liquid is played circulation with magnetic drive pump respectively, and flow all is 5.0L/min.The electrolytic cell galvanization is carried out electrolysis, and current density is 0.033A/cm
2, reaction temperature is controlled at 25 ± 2 ℃, and tank voltage is about 2.5～3.5V.Switch on after 10 hours, stop electrolysis.With platinum electrode the electrolyte before and after the electrolysis is carried out potential measurement, current potential respectively 0.25V and-0.50V.Get 10mL used for electrolyte iron hydrofining and carry out titration, the current efficiency that calculates is 24%.
Claims (8)
1. the method for a reducing sulfur dyes by electrocatalysis, described method comprises: be that negative electrode, inert electrode are anode with the silver electrode, in catholyte, add SULPHUR DYES, in catholyte under SULPHUR DYES initial concentration 1～500g/L condition, under 5～80 ℃, carry out electrolysis, SULPHUR DYES is reduced to water-soluble attitude.
2. the method for claim 1, it is characterized in that: the solvent of described catholyte is the mixture of water or water and organic solvent, described organic solvent is alcohol, oxolane, dimethyl formamide or the dimethylacetylamide of C1～C6; The electrolyte of described catholyte is alkali metal hydroxide, quaternary ammonium salt, alkali chloride or carbonate, and the electrolyte mass concentration is 0.4～40% in the catholyte.
3. method as claimed in claim 2 is characterized in that: the electrolyte mass concentration is 4～20% in the described catholyte.
4. the method for claim 1 is characterized in that described anode is a stainless steel anode.
5. the method for claim 1, the solvent that it is characterized in that described anolyte is the mixture of water or water and organic solvent, described organic solvent is alcohol, oxolane, dimethyl formamide or the dimethylacetylamide of C1～C6; The electrolyte of described catholyte is alkali metal hydroxide, quaternary ammonium salt, alkali chloride or carbonate, and the electrolyte mass concentration is 0.4～40% in the catholyte.
6. the method for claim 1, it is characterized in that: described electrolysis is carried out under 20～60 ℃, and current density is 0.01～1.00A/cm
2, tank voltage 2.5～5.5V, 2～100 hours conduction time.
7. as the described method of one of claim 1～6, it is characterized in that described silver electrode is an active silver electrode, described active silver electrode prepares as follows: in containing the anionic aqueous solution, earlier silver electrode is carried out anodic oxidation reactions, made electrode surface form the oxidation state layer of silver, again polarity of electrode is reversed, silver electrode is carried out cathodic reduction reaction, obtain described active silver electrode; Described anion is one or more the combination of halide ion and following anion: 1. perchlorate, 2. hypochlorite ion, 3. hydroxide ion, 4. nitrate ion, 5. sulfate ion, 6. carbanion, 7. organic acid ion, 8. phenolic hydroxyl group radical ion; Anion concentration is 0.01～20mol/L in the described aqueous solution.
8. method as claimed in claim 7, it is characterized in that: described active silver electrode prepares as follows: containing perchlorate 0.5～2mol/L, hydroxide ion 0.5～2mol/L, in the aqueous solution of nitrate ion 0.5～2mol/L, connect power anode with silver electrode, graphite electrode connects power cathode, in 20～60 ℃, under tank voltage 2.5～4.0V condition, silver electrode is carried out anodic oxidation reactions, electrode potential until silver electrode is 0.8～1.0V, again polarity of electrode is reversed, connect power cathode with silver electrode, graphite electrode connects power anode, in 20～60 ℃, under tank voltage 2.5～4.0V condition, silver electrode is carried out cathodic reduction reaction, until the electrode potential of silver electrode be-0.5～-0.8V, repeat described anodic oxidation reactions and cathodic reduction reaction 2～6 times, obtain described active silver electrode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604695A (en) * | 2017-09-26 | 2018-01-19 | 河北科技大学 | A kind of composite oxidant and its application method for sulfur dyeing |
| CN108693230A (en) * | 2018-05-25 | 2018-10-23 | 西安交通大学 | The device and method of sulphion concentration in a kind of quick detection strong alkali solution |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604695A (en) * | 2017-09-26 | 2018-01-19 | 河北科技大学 | A kind of composite oxidant and its application method for sulfur dyeing |
| CN107604695B (en) * | 2017-09-26 | 2019-12-10 | 河北科技大学 | Composite oxidant for sulfur dye dyeing and use method thereof |
| CN108693230A (en) * | 2018-05-25 | 2018-10-23 | 西安交通大学 | The device and method of sulphion concentration in a kind of quick detection strong alkali solution |
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| CN101349017B (en) | 2011-12-28 |
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