CN103739042A - Scandium doped stannic oxide micropore anode, preparation method and application thereof - Google Patents
Scandium doped stannic oxide micropore anode, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a scandium doped stannic oxide micropore anode, a preparation method and application thereof, belonging to the field of electrochemical water treatment technology. An mp-Ti plate is taken as a matrix, and SnO2-Sb and SnO2-Sb-Sc are sequentially arranged on the mp-Ti plate. The preparation method comprises steps of (1) preparing mixed solution of SbCl3 and SnCl4; (2) preparing mixed solution containing Sc, SbCl3 and SnCl4, pretreating a micropore titanium plate, then electroplating in the solution of step (1), then soaking the obtained product in the solution of step (2) and calcining at high temperature, finally, washing thoroughly by water and drying. The electrode is used for electrocatalytic oxidation of phenol in water, and has excellent capacity in removing and mineralizing phenol. The electrode prepared by the method has high catalytic activity, good stability and long service life, and has certain application prospect.
Description
Technical field
The present invention relates to a kind of micropore anode, relate in particular to a kind of tindioxide micropore anode, preparation method and application of scandium doping, belong to electro-chemical water processing technology field.
Background technology
Phenol is raw material and the intermediate of the industry production such as papermaking, coking, oil refining, plastics, agricultural chemicals, medicine is synthetic.Along with industrial expansion, the quantity discharged of phenolic wastewater is also increasing year by year.Phenolic wastewater is very serious to the harm of the mankind and other biological.The phenol of lower concentration can make protein denaturation, and the phenol of high density can make protein coagulating, and phenol can also cause people's nerve to sustain damage, until cause that whole body is poisoning.Environmental Protection Agency (USEPA) classifies phenolic compound as one of pollutent of preferential control, and China is also classified as the objectionable impurities of emphasis processing simultaneously.
At present, the treatment technology of phenolic waste water can be divided into physico-chemical process (salting-out process, absorption method, extraction process, membrane technique, ion exchange method etc.), biological process (activated sludge process, biomembrance process, anaerobic process, biotechnology of enzymes etc.) and chemical oxidization method (photochemical catalytic oxidation, ultrasound oxidation technology, Fenton reagent, ozone oxidation, wet oxidation, supercritical water oxidation, electrochemical oxidation etc.) three major types by action principle.Electro-chemical water treatment technology wherein because of its multifunctionality, be beneficial to environmental protection, easily be automated the superiority such as control, be called as " environmental friendliness " technology, day by day become the study hotspot in water pollution control field.
At electrochemical catalytic oxidation, process in the research of organic waste water Ti/PbO
2, Ti/SnO
2-Sb and Ti/BDD electrode get the attention.Due to Ti/PbO
2electrode may dissolve lead ion in electrolytic process, can cause the secondary pollution of water body, and Ti/BDD electrode prepares difficulty and involve great expense, and is unfavorable for industrial applications and development, so Ti/SnO
2-Sb electrode becomes electrochemical process and processes the main option of difficult for biological degradation organic waste water, but awaits in its catalytic activity and work-ing life continuing to improve.
Rear-earth-doped stannic oxide electrode has obtained a series of research in recent years, but the doping of the Sc of conduct " class boron " has no report always.Sc is bringing into play huge effect as a kind of of rare earth element Atom amount minimum aspect the inorganic chemistry such as stupalith, aspect the organic chemistry such as petrochemical complex, catalytic pyrolysis also because its superior catalytic performance is used widely, and show bright development prospect.
The present invention, take micropore titanium (mp-Ti) plate as matrix, adopts plating-dipping-sintering process, prepares Sc doping stannic oxide electrode, shows the advantage that the life-span is long, catalytic activity is high, has good application prospect.
Summary of the invention
The present invention aims to provide a kind of scandium doping stannic oxide electrode (mp-Ti/SnO efficiently catalyzing and oxidizing ability, take mp-Ti plate as matrix that has
2-Sb-Sc), preparation method, and be applied to the electrochemical oxidation of the hardly degraded organic substance such as phenol in water.
A kind of take mp-Ti plate as matrix, scandium doping stannic oxide electrode, is characterized in that, take mp-Ti plate as matrix, on mp-Ti plate, is followed successively by SnO
2-Sb and SnO
2-Sb-Sc, is designated as mp-Ti/SnO
2-Sb-Sc.Wherein Sb, Sc are equivalent to doping.
Above-mentioned one is take mp-Ti plate as matrix, and preparation method and the process of scandium doping stannic oxide electrode, comprise the following steps:
(1) by SbCl
3it is 36.5% that powder is dissolved in dense HCl(mass concentration, lower same) in, add a certain amount of SnCl
45H
2o, fully dissolves with appropriate dehydrated alcohol, and the volume ratio of dehydrated alcohol and dense HCl is 50:1, SnCl in the solution finally obtaining
4concentration is preferably 0.45～0.50mol/L, and Sn:Sb mol ratio is 100:(3～15), placement for some time is standby;
(2) by Scium trioxide (Sc
2o
3) powder is dissolved in dense HCl solution, heated and boiled is until powder dissolution adds a certain amount of SbCl
3, fully stir until dissolving adds a certain amount of SnCl
45H
2o, adds propyl carbinol, and ultrasonic boosting is dissolved, and the volume ratio of propyl carbinol and HCl solution is 20:1, SnCl in the solution finally obtaining
4concentration is preferably 0.80～0.85mol/L, and Sn:Sb:Sc mol ratio is 100:(3～15): (0.2～1), the steeping fluid placement of preparation is spent the night standby;
(3) by aperture, be that the mp-Ti plate of 10～80 microns embathes after oil removing in NaOH solution, boil with except oxide compound in oxalic acid solution, redistilled water cleans up, and nitrogen dries up standby;
(4) solution configuring take step (1) is as electroplate liquid, the mp-Ti plate of processing take step (3) is as negative electrode, platinum (Pt) sheet is anode, and middle layer is electroplated in constant current, after having electroplated, clean with distilled water flushing, in the baking oven of 105 ℃, place for some time until dry, put into 400 ℃～650 ℃ high-temperature calcination 1h of retort furnace, under room temperature after naturally cooling, clean with distilled water flushing, obtained SnO
2the mp-Ti/SnO in middle layer
2-Sb;
(5) what step (4) is obtained is coated with SnO
2the Ti/SnO in middle layer
2-Sb impregnated in the solution of (2) preparing (preferably at least 5min), then takes out and dries at room temperature, puts into baking oven and further dries; This process repeats, after 4～6 times, to put into 400 ℃～650 ℃ high-temperature calcination 1h of retort furnace, under room temperature after naturally cooling, rinses well with redistilled water;
(6) step (5) is repeated 3～5 times, last sintering time extends to 2h, is cooled to after room temperature, with redistilled water, rinses well, dries standbyly, obtains mp-Ti/SnO
2-Sb-Sc electrode.
In step (2), preferably Sn:Sb:Sc mol ratio is 100:6.5:(0.2～1).
With the mp-Ti/SnO of above-mentioned preparation
2-Sb-Sc electrode is anode, for the catalytic oxidation of water phenol.
Adopt electrode of the present invention to carry out the method for the catalytic oxidation of phenol: to adopt single groove electrolyzer, the Na that supporting electrolyte is 0.05mol/L
2sO
4solution, the starting point concentration of controlling phenol in water is preferably 50mg/L, phenol solution initial pH value 6.0～6.5, temperature of reaction is 25 ℃, with the mp-Ti/SnO preparing
2-Sb-Sc electrode is working electrode (anode), and Pt sheet is to electrode (negative electrode), adopts galvanostatic method, and current density is 10mA/cm
2, Pyrogentisinic Acid carries out catalytic oxidation.
Compared with prior art, the present invention has following beneficial effect:
1, to adopt mp-Ti plate be matrix in the present invention, has acidproof corrosion resistant advantage, and its microvoid structure provides large specific surface area simultaneously, for the raising of electrochemistry absorption and electrocatalysis characteristic provides material base.
2, the present invention has prepared Ti/SnO
2-Sb-Sc combined electrode (what main inventive point of the present invention was Sc adds).Sc is as unique element less than Sn atomic radius in rare earth element, and its introducing has changed composition and the surface tissue of catalyzer, has improved catalytic activity and the mechanical stability of electrode.
3, the electrode that the present invention prepares, for anode catalytic oxidation phenol, the clearance of phenol and organic mineralization rate (being TOC clearance) height, thus improved current efficiency, reduced energy consumption, industrial applications prospect is good, with the Ti/SnO without scandium doping
2-Sb electrode is compared, and the ability of removing phenol is strong, mineralization of organic material rate is high.And the prepared electrode catalyst activity of the present invention is high, good stability, long service life, and electrocatalysis is processed phenol in water and rapidly and efficiently, had certain application prospect.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) figure on Different electrodes surface: (a) be the mp-Ti matrix after pre-treatment; (b) mp-Ti/SnO preparing for embodiment 1
2-Sb-Sc electrode, in steeping fluid, Sn:Sb:Sc mol ratio is 100:6.5:0.5; (c) mp-Ti/SnO preparing for embodiment 2
2-Sb-Sc electrode, in steeping fluid, Sn:Sb:Sc mol ratio is 100:6.5:1; (d) mp-Ti/SnO preparing for embodiment 3
2-Sb-Sc electrode, in steeping fluid, Sn:Sb:Sc mol ratio is 100:6.5:0.25; (e) Ti/SnO preparing for comparative example
2-Sb electrode;
Fig. 2 is the linear volt-ampere scanning curve of embodiment and the prepared electrode of comparative example;
Fig. 3 reacts 4h phenol clearance and TOC mineralization rate in embodiment and comparative example.
Embodiment
The present invention is further illustrated in connection with accompanying drawing for embodiment below, but the present invention is not limited to following examples.
Embodiment 1:
1, the preparation of electroplate liquid: by SbCl
3powder is dissolved in dense HCl, adds a certain amount of SnCl
45H
2o, fully dissolves with dehydrated alcohol, and the volume ratio of dehydrated alcohol and dense HCl is 50:1, SnCl in the solution finally obtaining
4concentration is 0.45～0.50mol/L, and Sn:Sb mol ratio is 100:10, and placement for some time is standby.
2, the preparation of steeping fluid: by Scium trioxide (Sc
2o
3) powder is dissolved in appropriate dense HCl, boil until powder dissolution adds SbCl with electric furnace
3crystal, is stirred well to dissolving, adds SnCl
45H
2o crystal, adds a certain amount of propyl carbinol to dissolve, and under ultrasonic assisting, is heated to form the solution of stable homogeneous, and the volume ratio of propyl carbinol and dense HCl is 20:1, SnCl in the solution finally obtaining
4concentration is 0.80～0.85mol/L, and Sn:Sb:Sc mol ratio is 100:6.5:0.5, and the steeping fluid placement of preparation is spent the night standby.
3, the pre-treatment of mp-Ti base material: mp-Ti plate is dipped in the 40%NaOH of 80 ℃ and embathes 2h oil removing, be washed till neutrality with distilled water; Be dipped in 15% oxalic acid solution, keep 2h at 98 ℃, rinse well rear standbyly with redistilled water, Fig. 1 a is shown in by its SEM photo.
4, the solution configuring take step (1) is as electroplate liquid, and the mp-Ti plate of processing take step (3) is as negative electrode, and Pt sheet is anode, and internal layer is electroplated in constant current, and obtaining current density is 10mA/cm
2, electroplating time is 25min, in electroplating process, fully stirs.After plating completes, clean with distilled water flushing, in the baking oven of 100 ℃～105 ℃, place for some time until dry, put into 400 ℃ of retort furnaces (preferably 400 ℃ of high-temperature calcination 1h, after naturally cooling, clean with distilled water flushing under room temperature, obtain SnO
2middle layer.
What 5, step 4 is obtained is coated with SnO
2the Ti/SnO in middle layer
2-Sb impregnated in 5min in the solution of 2 preparations, dries at room temperature, places 10min and further dry in 105 ℃ of baking ovens; This process repeats, after 5 times, finally to put into 550 ℃ of high-temperature calcination 1h of retort furnace, under room temperature, after naturally cooling, with redistilled water, rinses well, dries.
6, step 5 is repeated 3～5 times, last sintering time extends to 2h, is cooled to after room temperature, with redistilled water, rinses well, dries standbyly, obtains mp-Ti/SnO
2-Sb-Sc electrode (electrode 1), Fig. 1 b is shown in by SEM photo.
7, catalytic activity test: at the H of 0.5mol/L
2sO
4in solution, take electrode 1 as working electrode, take Pt sheet as to electrode, with Hg/Hg
2sO
4electrode is that reference electrode carries out linear sweep voltammetry (LSV) test, and electric potential scanning scope is 1100～2000mV, and sweep velocity is 1mV/s.LSV scanning result is shown in Fig. 2, the reverse extending line of curve and the intersection point of transverse axis, the i.e. overpotential for oxygen evolution of electrode. the overpotential for oxygen evolution that records electrode 1 is 1.59V(vs Hg
2sO
4), higher than current reported electrode, illustrating under the same terms, it is less that the electrode of preparation is analysed oxygen side reaction, is more conducive to organic oxidation.
8, accelerated aging test: utilize constant current constant voltage source, take electrode 1 as anode, take Pt sheet as negative electrode, controlling plate spacing is 1cm, and current density is 100mA/cm
2, at 0.1molL
-1h
2sO
4in solution, measure, every a bath voltage of 0.5h record, until amplification exceedes 5V, think that electrode loses catalytic activity.Be 29h this electrode life, according to formula
if oxidation of phenol current density is 10mA/cm
2, be 2900h the electrode life in practical application.
9, the catalytic oxidation of phenol test: the electrocatalysis oxidation reaction of phenol carries out in single groove electrolyzer, the phenol solution that electrolytic solution is 60mL50mg/L, supporting electrolyte is 0.05mol/L Na
2sO
4solution, pH is neutral; The electrode 1 of preparing take step 5 is working electrode (anode), and Pt sheet is to electrode (negative electrode), and electrolytic solution stir speed (S.S.) is 400rpm, and current density is 10mA/cm
2, temperature of reaction is 25 ℃, and reaction times 4h the results are shown in Figure 3, and the clearance that the removal efficiency of phenol reaches 97.1%, TOC reaches 58.9%.
Embodiment 2:(Sn:Sc mol ratio is 100:1, and other conditions are with embodiment 1)
1, the preparation of electroplate liquid: by SbCl
3powder is dissolved in dense HCl, adds a certain amount of SnCl
45H
2o, fully dissolves with dehydrated alcohol, and the volume ratio of dehydrated alcohol and dense HCl is 50:1, SnCl in the solution finally obtaining
4concentration is 0.45-0.50mol/L, and Sn:Sb mol ratio is 100:10, and placement for some time is standby.
2, the preparation of steeping fluid: by Scium trioxide (Sc
2o
3) powder is dissolved in appropriate dense HCl, boil until powder dissolution adds SbCl with electric furnace
3crystal, is stirred well to dissolving, adds SnCl
45H
2o crystal, adds a certain amount of propyl carbinol to dissolve, and under ultrasonic assisting, is heated to form the solution of stable homogeneous, and the volume ratio of propyl carbinol and dense HCl is 20:1, SnCl in the solution finally obtaining
4concentration is 0.80～0.85mol/L, and Sn:Sb:Sc mol ratio is 100:6.5:1, and the steeping fluid placement of preparation is spent the night standby.
3, the pre-treatment of mp-Ti base material: mp-Ti plate is dipped in the 40%NaOH of 80 ℃ and embathes 2h oil removing, be washed till neutrality with distilled water; Be dipped in 15% oxalic acid solution, keep 2h at 98 ℃, rinse well rear standbyly with redistilled water, Fig. 1 a is shown in by its SEM photo.
4, the solution configuring take step (1) is as electroplate liquid, and the mp-Ti plate of processing take step (3) is as negative electrode, and Pt sheet is anode, and internal layer is electroplated in constant current, and obtaining current density is 10mA/cm
2, electroplating time is 25min, in electroplating process, fully stirs.After plating completes, clean with distilled water flushing, in the baking oven of 100 ℃～105 ℃, place for some time until dry, put into 400 ℃ of high-temperature calcination 1h of retort furnace, after naturally cooling, clean with distilled water flushing under room temperature, obtain SnO
2middle layer.
What 5, step 4 is obtained is coated with SnO
2the Ti/SnO in middle layer
2-Sb impregnated in 5min in the solution of 2 preparations, dries at room temperature, places 10min and further dry in 105 ℃ of baking ovens; This process repeats, after 5 times, to put into 550 ℃ of high-temperature calcination 1h of retort furnace, under room temperature, after naturally cooling, with redistilled water, rinses well, dries.
6, step 5 is repeated 3～5 times, last sintering time extends to 2h, is cooled to after room temperature, with redistilled water, rinses well, dries standbyly, obtains mp-Ti/SnO
2-Sb-Sc electrode (electrode 2), Fig. 1 c is shown in by SEM photo.
7, catalytic activity test: at the H of 0.5mol/L
2sO
4in solution, take electrode 1 as working electrode, take Pt sheet as to electrode, with Hg/Hg
2sO
4electrode is that reference electrode carries out LSV test, and electric potential scanning scope is 1100～2000mV, and sweep velocity is 1mV/s.LSV scanning result is shown in Fig. 2, and the overpotential for oxygen evolution that records electrode 2 is 1.57V(vs Hg
2sO
4).
8, the catalytic oxidation of phenol test: the electrocatalysis oxidation reaction of phenol carries out in single groove electrolyzer, the phenol solution that electrolytic solution is 60mL50mg/L, supporting electrolyte is 0.05mol/L Na
2sO
4solution, pH is neutral; The electrode 2 of preparing take step 5 is working electrode, and Pt sheet is to electrode, and electrolytic solution stir speed (S.S.) is 400rpm, and current density is 10mA/cm
2, temperature of reaction is 25 ℃, and reaction times 4h the results are shown in Figure 3, and the clearance that the removal efficiency of phenol reaches 91.6%, TOC reaches 41.1%.
Embodiment 3:(Sn:Sc mol ratio is 400:1, and other conditions are with embodiment 1)
1, the preparation of electroplate liquid: by SbCl
3powder is dissolved in dense HCl, adds a certain amount of SnCl
45H
2o, fully dissolves with dehydrated alcohol, and the volume ratio of dehydrated alcohol and dense HCl is 50:1, SnCl in the solution finally obtaining
4concentration is 0.45～0.50mol/L, and Sn:Sb mol ratio is 100:10, and placement for some time is standby.
2, the preparation of steeping fluid: by Scium trioxide (Sc
2o
3) powder is dissolved in appropriate dense HCl, boil until powder dissolution adds SbCl with electric furnace
3crystal, is stirred well to dissolving, adds SnCl
45H
2o crystal, adds a certain amount of propyl carbinol to dissolve, and under ultrasonic assisting, is heated to form the solution of stable homogeneous, and the volume ratio of propyl carbinol and dense HCl is 20:1, SnCl in the solution finally obtaining
4concentration is 0.80～0.85mol/L, and Sn:Sb:Sc mol ratio is 100:6.5:0.25, and the steeping fluid placement of preparation is spent the night standby.
3, the pre-treatment of mp-Ti base material: mp-Ti plate is dipped in the 40%NaOH of 80 ℃ and embathes 2h oil removing, be washed till neutrality with distilled water; Be dipped in 15% oxalic acid solution, keep 2h at 98 ℃, rinse well rear standbyly with redistilled water, Fig. 1 a is shown in by its SEM photo.
4, the solution configuring take step (1) is as electroplate liquid, and the mp-Ti plate of processing take step (3) is as negative electrode, and Pt sheet is anode, and internal layer is electroplated in constant current, and obtaining current density is 10mA/cm
2, electroplating time is 25min, in electroplating process, fully stirs.After plating completes, clean with distilled water flushing, in the baking oven of 100 ℃～105 ℃, place for some time until dry, put into 400 ℃～650 ℃ of retort furnaces (preferably 400 ℃) high-temperature calcination 1h, after naturally cooling, clean with distilled water flushing under room temperature, obtain SnO
2middle layer.
What 5, step 4 is obtained is coated with SnO
2the Ti/SnO in middle layer
2-Sb impregnated in 5min in the solution of 2 preparations, dries at room temperature, places 10min and further dry in 105 ℃ of baking ovens; This process repeats, after 5 times, to put into 400 ℃～650 ℃ of retort furnaces (preferably 550 ℃) high-temperature calcination 1h, under room temperature, after naturally cooling, with redistilled water, rinses well, dries.
6, step 5 is repeated 3～5 times, last sintering time extends to 2h, is cooled to after room temperature, with redistilled water, rinses well, dries standbyly, obtains mp-Ti/SnO
2-Sb-Sc electrode (electrode 3), Fig. 1 d is shown in by SEM photo.
7, catalytic activity test: at the H of 0.5mol/L
2sO
4in solution, take electrode 3 as working electrode, take Pt sheet as to electrode, with Hg/Hg
2sO
4electrode is that reference electrode carries out LSV test, and electric potential scanning scope is 1100～2000mV, and sweep velocity is 1mV/s.LSV scanning result is shown in Fig. 2, and the overpotential for oxygen evolution that records electrode 3 is 1.52V(vs Hg
2sO
4).
8, the catalytic oxidation of phenol test: the electrocatalysis oxidation reaction of phenol carries out in single groove electrolyzer, the phenol solution that electrolytic solution is 60mL50mg/L, supporting electrolyte is 0.05mol/L Na
2sO
4solution, pH is neutral; The electrode 1 of preparing take step 5 is working electrode, and Pt sheet is to electrode, and electrolytic solution stir speed (S.S.) is 400rpm, and current density is 10mA/cm
2, temperature of reaction is 25 ℃, and reaction times 4h the results are shown in Figure 3, and the clearance that the removal efficiency of phenol reaches 82.6%, TOC reaches 32.4%.
Comparative example: (Sc that do not adulterate, the same embodiment of other conditions)
1, the configuration of electroplate liquid: same embodiment.
2, the preparation of steeping fluid: by SbCl
3be dissolved in a small amount of dense HCl, be stirred well to dissolving, add SnCl
45H
2o and a certain amount of propyl carbinol dissolve, ultrasonic boosting, and the solution of formation stable homogeneous, the volume ratio of propyl carbinol and dense HCl is 20:1, SnCl in the solution finally obtaining
4concentration is 0.80～0.85mol/L, and Sn:Sb mol ratio is 100:6.5, and the steeping fluid placement of preparation is spent the night standby.
3, the pre-treatment of mp-Ti base material: with embodiment 1.
4, according to the step 4,5,6 of embodiment, prepare mp-Ti/SnO
2-Sb(comparison electrode), 1e is shown in by SEM photo.
5, catalytic activity test: the LSV condition of comparison electrode is with embodiment step 7, and LSV scanning result is shown in Fig. 2, and the overpotential for oxygen evolution of comparison electrode is 1.50V(vs Hg
2sO
4).
6, accelerated aging test: with embodiment step 8, be 21h electrode life, according to formula
if oxidation of phenol current density is 10mA/cm
2, be 2100h the electrode life in practical application.
7, the catalytic oxidation of phenol test: take comparison electrode as working electrode, oxidation of phenol condition is identical with the step 9 of embodiment, the results are shown in Figure the clearance of phenol after 3,4h is that 79.3%, TOC mineralization rate is 38.0%.
The result of embodiment and comparative example relatively shows, with respect to the stannic oxide electrode without Sc doping, and the stannic oxide electrode (mp-Ti/SnO of doping Sc
2-Sb-Sc electrode), catalytic activity and work-ing life obviously improve.Mp-Ti/SnO
2-Sb-Sc electrode has that overpotential for oxygen evolution is high, the ability of long service life, removal phenol is strong and mineralization of organic material rate advantages of higher.Therefore, there is the prospect of good processing organic wastewater with difficult degradation thereby.
Claims (7)
1. take micropore titanium (mp-Ti) plate as a matrix, scandium doping stannic oxide electrode, is characterized in that, take mp-Ti plate as matrix, on mp-Ti plate, is followed successively by SnO
2-Sb and SnO
2-Sb-Sc.
2. preparation one claimed in claim 1 is take mp-Ti plate as matrix, and the method for scandium doping stannic oxide electrode, is characterized in that, comprises the following steps:
(1) by SbCl
3powder is dissolved in dense HCl, adds a certain amount of SnCl
45H
2o, fully dissolves with appropriate dehydrated alcohol, and the volume ratio of dehydrated alcohol and dense HCl is 50:1, and Sn:Sb mol ratio is 100:(3～15), place for some time standby;
(2) by Scium trioxide (Sc
2o
3) powder is dissolved in dense HCl solution, heated and boiled is until powder dissolution adds a certain amount of SbCl
3, fully stir until dissolving adds a certain amount of SnCl
45H
2o, adds propyl carbinol, and ultrasonic boosting is dissolved, and the volume ratio of propyl carbinol and HCl solution is 20:1, and Sn:Sb:Sc mol ratio is 100:(3～15): (0.2～1), the steeping fluid placement of preparation is spent the night standby;
(3) by aperture, be that the mp-Ti plate of 10～80 microns embathes after oil removing in NaOH solution, boil with except oxide compound in oxalic acid solution, redistilled water cleans up, and nitrogen dries up standby;
(4) solution configuring take step (1) is as electroplate liquid, the mp-Ti plate of processing take step (3) is as negative electrode, platinized platinum (Pt) is anode, and middle layer is electroplated in constant current, after having electroplated, clean with distilled water flushing, in the baking oven of 105 ℃, place for some time until dry, put into 400 ℃～650 ℃ high-temperature calcination 1h of retort furnace, under room temperature after naturally cooling, clean with distilled water flushing, obtained SnO
2the mp-Ti/SnO in middle layer
2-Sb;
(5) what step (4) is obtained is coated with SnO
2the Ti/SnO in middle layer
2-Sb impregnated in the solution of (2) preparing (preferably at least 5min), then takes out and dries at room temperature, puts into baking oven and further dries; This process repeats, after 4～6 times, to put into 400 ℃～650 ℃ high-temperature calcination 1h of retort furnace, under room temperature after naturally cooling, rinses well with redistilled water;
(6) step (5) is repeated 3～5 times, last sintering time extends to 2h, is cooled to after room temperature, with redistilled water, rinses well, dries standbyly, obtains mp-Ti/SnO
2-Sb-Sc electrode.
3. according to the method for claim 2, it is characterized in that, in step (2), Sn:Sb:Sc mol ratio is 100:6.5:(0.2～1).
4. according to the method for claim 2, it is characterized in that SnCl in the solution finally obtaining in step (1)
4concentration is 0.45～0.50mol/L.
5. according to the method for claim 2, it is characterized in that SnCl in the solution finally obtaining in step (2)
4concentration is 0.80～0.85mol/L.
6. take electrode claimed in claim 1 as anode, for the catalytic oxidation of water phenol.
Take electrode claimed in claim 1 as anode for the method for the catalytic oxidation of water phenol, it is characterized in that, comprise the following steps:
Adopt single groove electrolyzer, the Na that supporting electrolyte is 0.05mol/L
2sO
4solution, initial pH value 6.0～6.5, temperature of reaction is 25 ℃, and take the electrode of claim 1 as working electrode, Pt sheet is to electrode, adopts galvanostatic method, and Pyrogentisinic Acid carries out catalytic oxidation.
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| CN101124852A (en) * | 2004-09-23 | 2008-02-13 | 3M创新有限公司 | Organic electroluminescent device |
| CN101861412A (en) * | 2007-11-16 | 2010-10-13 | 阿克佐诺贝尔股份有限公司 | Electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101124852A (en) * | 2004-09-23 | 2008-02-13 | 3M创新有限公司 | Organic electroluminescent device |
| CN101861412A (en) * | 2007-11-16 | 2010-10-13 | 阿克佐诺贝尔股份有限公司 | Electrode |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106395999A (en) * | 2016-11-01 | 2017-02-15 | 北京工业大学 | Ni-doped tin dioxide microporous anode, preparation method and application |
| CN106395999B (en) * | 2016-11-01 | 2019-10-15 | 北京工业大学 | A kind of nickel doping stannic oxide micropore anode, preparation method and application |
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