CN103614712B - Sol-gel process is prepared Sb, Ce codope SnO2The method in intermediate layer - Google Patents
Sol-gel process is prepared Sb, Ce codope SnO2The method in intermediate layer Download PDFInfo
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Abstract
The invention discloses a kind of sol-gel process and prepare Sb, Ce codope SnO2The method in intermediate layer, belongs to electrode activity improving technology field. Step of the present invention is: step 1, titanium matrix is carried out to pretreatment; Step 2, obtain solution A; Step 3, obtain solution B; Step 4, solution B is added drop-wise in solution A, after continuing to stir, fully mixing, under room temperature, ageing forms colloidal sol; Step 5, the colloidal sol that the pretreated titanium matrix of process step 1 is made by step 4 carry out film, heat treatment, make the SnO of required doping Sb, Ce2Intermediate layer. Sb, Ce codope SnO prepared by the present invention2Novel lead dioxide electrode intermediate layer, can effectively improve titanium matrix and PbO2The adhesion of active layer, makes electrode performance good, long service life.
Description
Technical field
The present invention relates to electrode activity improving technology field, more particularly, relate to one and prepare Sb, Ce codope SnO by sol-gel process2The method in novel lead dioxide electrode intermediate layer.
Background technology
In recent years, with TiO2For the semiconductor photoelectrocatalysielectrode technology of representative becomes the research forward position of domestic and international water treatment technology and develops focus. The tin ash coated anode of making on titanium matrix has the features such as overpotential for oxygen evolution is high, catalytic activity is good, is conventionally considered to aspect organic anodic oxidation and wastewater treatment, to have good application prospect. Titanium has good electric conductivity, corrosion resistance, the superior advantage such as biocompatibility and higher voidage, has obtained application comparatively widely and research. For example, the people such as E.Fockedey have prepared titanium foam Ji Xi-antimonial modified electrode, and have studied anode and the impact of negative electrode associated treatment on organic removal rate in waste water.
SnO2Be N-shaped semiconductor material with wide forbidden band, there is wider valence band width (3.87-4.3eV), but pure SnO2The resistance of film is conventionally higher, and its carrier concentration is determined only in the time of high temperature, just have desirable electric conductivity and more difficult control by oxygen room. And doping SnO2Material can improve the electrical conductivity of material, thereby electrode doping SnO2In Optical Electro-Chemistry, be used widely.
General passing through at SnO2In mix a small amount of Sb, F, In or Pb plasma and reduce SnO2Resistivity and keep it to there is good visible light transmissivity. Doping SnO2Film, with its good optics, electric property and high chemical stability, is widely used in the fields such as solar cell, liquid crystal display (LCD), electroluminescent and low-E glass for building. Recent study is found, containing a small amount of SnO2DSA electrode or with doping SnO2Be main SnO2Coating DSA electrode, the electrocatalysis that organic matter anodic oxidation and wastewater treatment have all been had, has caused researcher's very big concern.
At present, external research majority in this regard, still in the evaluation phase to the organic degradation effect of selected target, is more common in the degraded to aromatic compound. Adulterate different elements to SnO2The impact of electrical conductivity and the impact of organic matter electrochemical degradation mechanism is all lacked to further research and demonstration.
Through retrieval, domestic more existing technical schemes are in this regard open, as China Patent No. ZL200610147403.4, Granted publication day is on December 24th, 2008, invention and created name is: for Nanomter electrode with high oxygen-separating potential and long life of sewage disposal and preparation method thereof, this application case relates to a kind of tin antimony cerium europium composite oxides nano-electrode and preparation method. Formed by titanium metal plate area load tin, antimony, cerium, europium nano composite oxide decorative layer. Be prepared by so-gel method and in conjunction with temperature programmed oxidation roasting technique. The nano-electrode of this application case has the advantages such as oxygen evolution potential is high, long service life simultaneously. The multiple rare earth metal composition but this application case has been adulterated, manufacturing cost is high. Chinese Patent Application No. 201210177931.X, the applying date is on May 31st, 2012, invention and created name is: a kind of Ce doped titanium-base SnO2The processing method of the preparation method of electrode and metronidazole waste water; This application case discloses a kind of Ce doped titanium-base SnO2The preparation method of electrode, comprises the following steps: 1) titanium matrix is carried out to pretreatment through polishing, alkali cleaning, pickling successively; 2) will impregnated in masking liquid through pretreated titanium matrix, then heat-treat; Wherein, in described masking liquid, solute comprises the soluble salt of Sn, Sb, Ce. This application pattern electrode manufacture craft is simple, effectively stops the generation of passivation layer titanium dioxide. But preparation technology is more complicated for this application case, still needs further improvement.
Summary of the invention
1. the technical problem that invention will solve
The object of the invention is to prepare Sb, Ce codope SnO by sol-gel process2Novel lead dioxide electrode intermediate layer, utilizes this intermediate layer effectively to improve titanium matrix and PbO2The adhesion of active layer, improves electrode stability, and then improves titanium base PbO2In the life-span of electrode, improve the performance of electrode.
2. technical scheme
For achieving the above object, technical scheme provided by the invention is:
Sol-gel process of the present invention is prepared Sb, Ce codope SnO2The method in intermediate layer, the steps include:
Step 1, titanium matrix is carried out to pretreatment:
Titanium matrix, with after sand papering, is used to acetone, absolute ethanol washing oil removing successively, then pass through acid etching, supersound washing, dry for standby;
Step 2, obtain solution A:
Absolute ethyl alcohol is divided into isopyknic two parts, a absolute ethyl alcohol is mixed with acetylacetone,2,4-pentanedione, under stirring condition, add butyl titanate, after fully mixing, add another part of absolute ethyl alcohol, continue to stir, fully mix wiring solution-forming A;
Step 3, obtain solution B:
(1) take pink salt, antimonic salt and cerium salt;
(2) pink salt, antimonic salt and the cerium salt that step (1) are taken are dissolved in concentrated hydrochloric acid, add successively absolute ethyl alcohol and salpeter solution, after fully mixing, add acetamide, continue to stir;
(3) configuration citric acid solution, fully mixes citric acid solution with the solution that step (2) makes;
(4) under stirring condition, in step (3) gained solution, add distilled water, and use ammoniacal liquor to regulate pH, leave standstill, after ageing, add polyethylene glycol, mix wiring solution-forming B;
Step 4, solution B is added drop-wise in solution A, after continuing to stir, fully mixing, under room temperature, ageing forms colloidal sol;
Step 5, the colloidal sol that the pretreated titanium matrix of process step 1 is made by step 4 carry out film, heat treatment, make described Sb, Ce codope SnO2Intermediate layer.
Further, the matrix adopting of titanium described in step 1 TA1The pure titanium metal of type.
Further, the absolute ethyl alcohol using in step 2 removes through 4A molecular sieve the minor amount of water containing, and in solution A, the mol ratio of butyl titanate, absolute ethyl alcohol, water and acetylacetone,2,4-pentanedione is 5:8:0.6:0.5.
Further, the pink salt described in step (1) is SnCl2·2H2O, antimonic salt is SbCl3, cerium salt is Ce (NO3)3·6H2O; In pink salt, antimonic salt and the cerium salt taking, the mol ratio of Sn, Sb, Ce is 100:6:0.3.
The mol ratio of the solution total amount that further, in step (3), citric acid solution and step (2) make is 1:1.
The mol ratio of the distillation water yield further, adding in step (4) and step (3) gained solution total amount is 36:1; Using ammoniacal liquor to regulate pH is 1～2.
Further, in step 4, the rate of addition of solution B is 12/min, continues to stir 30min.
Further, in step 5, be coated with membrane operations by be immersed in 50～70s in the colloidal sol that step 4 makes through step 1 pretreated titanium matrix, titanium matrix is lifted out from described colloidal sol, put into baking oven dry 10～15min at 100～120 DEG C, repeat after film, drying process 5 times, put into chamber type electric resistance furnace and heat-treat 1h, heat treatment temperature is 400 DEG C; Repeat, after film, drying process 5 times, again to put into chamber type electric resistance furnace and heat-treat 1h, heat treatment temperature is also 400 DEG C; Repeat film, drying process 5 times again, put into for the third time chamber type electric resistance furnace and heat-treat 3h, heat treatment temperature is 500 DEG C.
3. beneficial effect
Adopt technical scheme provided by the invention, compared with existing known technology, there is following remarkable result and adopt
(1) sol-gel process of the present invention is prepared Sb, Ce codope SnO2The method in intermediate layer, the electrode intermediate layer of preparation covers titanium matrix completely, and arranges closely, and crystal grain is small, and crystal formation is full, belongs to rutile-type, and specific area is larger, can effectively improve titanium matrix and PbO2The adhesion of active layer, avoids PbO2Active layer comes off, and prevents the passivation of titanium matrix, and then improves electro catalytic activity and the service life of PbO2 electrode;
(2) sol-gel process of the present invention is prepared Sb, Ce codope SnO2The method in intermediate layer, method is simple, and low cost of manufacture has good using value.
Detailed description of the invention
For further understanding content of the present invention, below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The sol-gel process of the present embodiment is prepared Sb, Ce codope SnO2The method in intermediate layer, the steps include:
Step 1, titanium matrix is carried out to pretreatment:
By titanium matrix with 600 order emery papers polishings smooth surfaces as mirror after, successively with acetone, the ultrasonic processing of absolute ethanol washing 10min oil removing, putting into volume ratio is the HF(hydrofluoric acid of 1:4 again) and the mixed solution of ethylene glycol corrode 1min, titanium matrix through acid etching is put into intermediate water (redistilled water), acetone, the each supersound washing 10min of absolute ethyl alcohol successively, then wash down by deionized water, flushing 1min post-drying is for subsequent use. Described titanium matrix adopting TA1The pure titanium metal of type, purity is 99.5%.
Step 2, obtain solution A:
Absolute ethyl alcohol is divided into isopyknic two parts, a absolute ethyl alcohol is mixed with acetylacetone,2,4-pentanedione, under intense agitation, slowly add butyl titanate (C16H36O4Ti), after fully mixing, add another part of absolute ethyl alcohol, continue to stir 30min, fully mix wiring solution-forming A; In solution A, the mol ratio of butyl titanate, absolute ethyl alcohol, water and acetylacetone,2,4-pentanedione is 5:8:0.6:0.5. The absolute ethyl alcohol using removes minor amount of water through 4A molecular sieve, and the present embodiment is strictly controlled the water content in absolute ethyl alcohol, to guarantee that configuration obtains the solution A of ideal performance.
Step 3, obtain solution B:
(1) take pink salt, antimonic salt and cerium salt: pink salt is SnCl2·2H2O, antimonic salt is SbCl3, cerium salt is Ce (NO3)3·6H2O; In pink salt, antimonic salt and the cerium salt taking, the mol ratio of Sn, Sb, Ce is 100:6:0.3.
(2) it is, in 37.5% concentrated hydrochloric acid, to add successively 2ml absolute ethyl alcohol and salpeter solution that pink salt, antimonic salt and cerium salt step (1) being taken is dissolved in a small amount of concentration, obtains adding a small amount of acetamide after mixed alcohol solution, continues to stir.
(3) citric acid solution of configuration 2.14molL, on the basis that is 1:1 mixes two kinds of solution in the mol ratio that ensures the solution that citric acid solution consumption makes with step (2).
(4) under stirring condition, in step (3) gained solution, add distilled water, the mol ratio of the distillation water yield adding and step (3) gained solution total amount is 36:1, and use ammoniacal liquor regulate pH be 1, leave standstill, after ageing 3h, the protective agent polyethylene glycol that adds appropriate inhibition to reunite, mixes wiring solution-forming B;
Step 4, solution B is added drop-wise in solution A with the speed of 12/min, continues to stir 30min, after fully mixing, form the yellow solution of homogeneous transparent, under room temperature, ageing forms colloidal sol;
Step 5, be coated with membrane operations by be immersed in 50～55s in the colloidal sol that step 4 makes through step 1 pretreated titanium matrix, titanium matrix is lifted out with certain speed from described colloidal sol, put into baking oven dry 10min at 100～105 DEG C, repeat after film, drying process 5 times, put into chamber type electric resistance furnace and heat-treat 1h, heat treatment temperature is 400 DEG C; Repeat, after film, drying process 5 times, again to put into chamber type electric resistance furnace and heat-treat 1h, heat treatment temperature is also 400 DEG C; Repeat film, drying process 5 times again, put into for the third time chamber type electric resistance furnace and heat-treat 3h, heat treatment temperature is 500 DEG C, to ensure coating exhaustive oxidation. Make the SnO of required doping Sb, Ce, Ti2Intermediate layer. The SnO obtaining through the present embodiment film, heat treatment operation2Intermediate layer can cover titanium matrix completely, and arranges closely.
At Sb doping SnO2In coated electrode, adulterate some special metal or nonmetalloids, not only can change the electrical property of coating, and can affect the electro catalytic activity of coating. The interpolation of rare earth oxide, in layer semiconductor energy gap, introducing deep-level impurity therein can be with, this structure is similar to adds the impurity such as Si, P formation semiconductor energy gap in semi-conducting material, these can, with a passage that energy level is lower is provided for the transmission of electronics, be conducive to further improve the electrical property of electrode material. In addition, the 4f electronic structure that rare earth element is special, makes rare earth atom very easily because deformation occurs in polarization, thereby enter tin-antimony oxide intracell in the mode of calking or displacement, in semi-conducting material, form defect, as room, hole etc., these defects are very large on the impact of electrode material character. Due to SnO2There is higher electrical conductivity, mechanical strength and good decay resistance, can form Ti, Sn intermetallic compound with titanium matrix, therefore can strengthen the adhesive force of matrix and active coating as intermediate layer, avoid coating shedding, prevent the passivation of titanium matrix. It is matrix that the present embodiment adopts titanium electrode, with butyl titanate, and SnCl2·2H2O，SbCl3For presoma, prepare Sb, Ti and rare earth codope SnO by sol-gel process2Intermediate layer. The electrode intermediate layer of preparation covers titanium matrix completely, and arranges closely, and crystal grain is small, and crystal formation is full, belongs to rutile-type, and specific area is larger, can effectively improve titanium matrix and PbO2The adhesion of active layer, avoids PbO2Active layer comes off, and prevents the passivation of titanium matrix, and then improves electro catalytic activity and the service life of PbO2 electrode. SnO2Film has multiple preparation method, common are sputtering method, thermal spray deposition method, chemical vapour deposition technique (CVD), electron beam vacuum vapor deposition method. The present embodiment adopts traditional sol-gel process, by the control to its relevant parameter, has obtained Optimization Technology, and method is simple, and low cost of manufacture has good using value.
Embodiment 2
The sol-gel process of the present embodiment is prepared Sb, Ce codope SnO2The method in intermediate layer, with embodiment 1, difference is substantially: it is 1.5 that step when obtain solution B (4) is used ammoniacal liquor regulator solution pH; In step 5, each film, drying process are: by be immersed in 55～60s in the colloidal sol that step 4 makes through the pretreated titanium matrix of step 1, titanium matrix is lifted out from described colloidal sol, put into baking oven dry 12min at 110～115 DEG C.
Embodiment 3
The sol-gel process of the present embodiment is prepared Sb, Ce codope SnO2The method in intermediate layer, with embodiment 1, difference is substantially: it is 2 that step when obtain solution B (4) is used ammoniacal liquor regulator solution pH; In step 5, each film, drying process are: by be immersed in 60～70s in the colloidal sol that step 4 makes through the pretreated titanium matrix of step 1, titanium matrix is lifted out from described colloidal sol, put into baking oven dry 15min at 115～120 DEG C.
Sol-gel process described in embodiment 1～3 is prepared Sb, Ce codope SnO2The method in intermediate layer, method is simple, low cost of manufacture, titanium matrix and PbO can effectively be improved in the intermediate layer of preparation2The adhesion of active layer, improves electrode stability, and then improves titanium base PbO2In the life-span of electrode, improve the performance of electrode.
Claims (1)
1. sol-gel process is prepared Sb, Ce codope SnO2The method in intermediate layer, the steps include:
Step 1, titanium matrix is carried out to pretreatment:
By TA1The pure titanium metal matrix of type, with after sand papering, is used successively acetone, absolute ethanol washing oil removing, then is passed through acid etchingQuarter, supersound washing, dry for standby;
Step 2, obtain solution A:
Absolute ethyl alcohol is divided into isopyknic two parts, a absolute ethyl alcohol is mixed with acetylacetone,2,4-pentanedione, under stirring condition, add titaniumAcid four butyl esters, after fully mixing, add another part of absolute ethyl alcohol, continue to stir, and fully mix wiring solution-forming A; Wherein, instituteWith absolute ethyl alcohol remove the minor amount of water containing, butyl titanate, absolute ethyl alcohol, water and second in solution A through 4A molecular sieveThe mol ratio of acyl acetone is 5:8:0.6:0.5;
Step 3, obtain solution B:
(1) take pink salt, antimonic salt and cerium salt; Described pink salt is SnCl2·2H2O, antimonic salt is SbCl3, cerium salt is Ce (NO3)3·6H2O; In pink salt, antimonic salt and the cerium salt taking, the mol ratio of Sn, Sb, Ce is 100:6:0.3;
(2) pink salt, antimonic salt and the cerium salt that step (1) are taken are dissolved in concentrated hydrochloric acid, add successively absolute ethyl alcohol and salpeter solution,After fully mixing, add acetamide, continue to stir;
(3) configuration citric acid solution, fully mixes citric acid solution with the solution that step (2) makes;
(4) under stirring condition, in step (3) gained solution, add distilled water, the distillation water yield adding and step (3) gainedThe mol ratio of solution total amount is 36:1; And use ammoniacal liquor to regulate pH to be 1～2, to leave standstill, after ageing, add polyethylene glycol, mixedClose even wiring solution-forming B;
Step 4, solution B is added drop-wise in solution A, the rate of addition of solution B is 12/min, continue to stir 30min,After fully mixing, under room temperature, ageing forms colloidal sol;
Step 5, carry out film behaviour by be immersed in 50～70s in the colloidal sol that step 4 makes through step 1 pretreated titanium matrixDo, titanium matrix is lifted out from described colloidal sol, put into baking oven dry 10～15min at 100～120 DEG C, repetition film,After drying process 5 times, put into chamber type electric resistance furnace and heat-treat 1h, heat treatment temperature is 400 DEG C; Repeat film, dryOperate after 5 times, again put into chamber type electric resistance furnace and heat-treat 1h, heat treatment temperature is also 400 DEG C; Repeat again film,Drying process 5 times, puts into for the third time chamber type electric resistance furnace and heat-treats 3h, and heat treatment temperature is 500 DEG C, described in makingSb, Ce codope SnO2Intermediate layer.
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| CN104556193B (en) * | 2015-01-19 | 2016-08-24 | 陕西科技大学 | Hot assisting sol-the gel method of a kind of employing prepares Sm2o3/ SnO2the method of nano-complex |
| CN108046380B (en) * | 2017-12-13 | 2021-02-12 | 东华大学 | Titanium-based Sn-Sb-Ce oxide electrode and preparation method and application thereof |
| CN109772295B (en) * | 2019-03-11 | 2020-09-08 | 中南大学 | Bismuth tungstate modified antimony-doped tin dioxide composite photoelectric catalytic electrode, preparation method and application |
| CN113754026B (en) * | 2021-10-13 | 2023-05-16 | 东莞理工学院 | High-stability SnO for water treatment 2 Preparation method of-Sb electrode |
| CN115626693B (en) * | 2022-12-22 | 2023-04-28 | 深圳永清水务有限责任公司 | Lead-antimony coated titanium anode plate with intermediate layer and preparation method and application thereof |
| CN115676983B (en) * | 2022-12-29 | 2023-05-02 | 深圳永清水务有限责任公司 | Lead-antimony coated titanium anode with cerium doped intermediate layer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659224A (en) * | 2012-05-30 | 2012-09-12 | 北京师范大学 | Preparation method and application of nano coated electrode |
| CN102701329A (en) * | 2012-07-17 | 2012-10-03 | 北京师范大学 | Preparation method of porous nanometer crystal electrodes and application of porous nanometer crystal electrodes |
| CN102701333A (en) * | 2012-05-31 | 2012-10-03 | 华南师范大学 | Preparation method of Ce (cerium) doped titanium base SnO2 (stannic oxide) electrodes and metronidazole wastewater treatment method |
Family Cites Families (1)
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659224A (en) * | 2012-05-30 | 2012-09-12 | 北京师范大学 | Preparation method and application of nano coated electrode |
| CN102701333A (en) * | 2012-05-31 | 2012-10-03 | 华南师范大学 | Preparation method of Ce (cerium) doped titanium base SnO2 (stannic oxide) electrodes and metronidazole wastewater treatment method |
| CN102701329A (en) * | 2012-07-17 | 2012-10-03 | 北京师范大学 | Preparation method of porous nanometer crystal electrodes and application of porous nanometer crystal electrodes |
Non-Patent Citations (2)
| Title |
|---|
| 稀土掺杂PbO2电极的制备及催化性能研究;范洪富等;《中国稀土学报》;20070630;第25卷(第3期);第300页"1.2中间层制备" * |
| 钛基氧化物阳极中间层的研究进展;宋秀丽等;《电化学》;20130831;第19卷(第4期);第314页"1氧化物固溶体中间层的特性" * |
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