CN101746850A - Multi-dimensional nanomaterial micro-current electron exciting electrode and preparation method thereof - Google Patents
Multi-dimensional nanomaterial micro-current electron exciting electrode and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a multi-dimensional nanomaterial micro-current electron exciting electrode, which comprises the following steps: a) pre-treating a titanium substrate of the electrode; b) culturing a nano-titanium dioxide crystal layer with the phase ratio of anatase to rutile of 2:8-7:3 on the substrate of the electrode by controlling the processing temperature; and c) sintering a layer of metal oxide nano-coating with a plurality of components which are mixed according to a certain proportion on the surface of the titanium dioxide crystal layer of the electrode. The invention further provides the multi-dimensional nanomaterial micro-current electron exciting electrode prepared by applying the method, the surface coating of the electrode is coated on the surface of the mixed nano-titanium dioxide crystal bottom layer with a certain proportion of rutile, and the multi-dimensional nanomaterial micro-current electron exciting electrode is a stereo multi-dimensional structure. The electrode has large specific surface area, high catalytic activity and good conductivity.
Description
Technical field
The present invention relates to a kind of multi-dimensional nanomaterial micro-current electron exciting electrode, especially also relate to the preparation method of described electrode.Belong to the Electrochemical Engineering field.
Background technology
High-level oxidation technology is the emerging technology of the pollutent of the poisonous and bio-refractory of the processing that grew up in recent years.The outstanding feature of advanced oxidation processes is to be that main oxygenant and organism react with hydroxyl radical free radical, the organic free radical that generates in the reaction can continue to participate in the chain reaction of HO, by after generating the organic peroxy free radical, oxidative decomposition further takes place until being degraded to final product CO perhaps
2And H
2O, thus reach the organic purpose of oxygenolysis.Compare with other traditional water treatment method, advanced oxidation processes has following characteristics: produce very active in a large number its oxidation capacity of hydroxyl radical free radical HO (2.80v) and be only second to fluorine (2.87), it is as the intermediate product of reaction, can bring out the chain reaction of back, hydroxyl radical free radical differs very little with the reaction rate constant of different organic substances, when having multiple pollutent in the water, a kind of material can not occur and be degraded and the constant substantially situation of another kind of material; HO can't be selectively directly reacts with pollutants in waste water it is degraded to carbonic acid gas, water and harmless object, can not produce secondary pollution; The general chemistry oxidation style is because oxidation capacity is poor, react reason such as selective, often can not directly reach and remove the purpose that organism reduces TOC and COD fully, and there is not this problem substantially in the advanced oxidation rule, intermediate product in the oxidising process all can continue with the hydroxyl free radical reaction, be oxidized to carbonic acid gas and water until at last fully, thereby reached the thorough purpose of removing TOC, COD; Because it is a kind of physical and chemical process, be easy to be controlled, handle needs to satisfy, even can reduce the pollutent of 10-9 level; Compare with common chemical oxidization method, the speed of response of advanced oxidation processes is very fast, and general reaction rate constant can reach processing requirements greater than 109mol-1Ls-1 in very short time; Both can be used as individual curing, can be complementary with other treating processess again,, can reduce processing cost as pre-treatment as biochemical treatment.
Also can pass through the ultraviolet technology degradation of organic substances.It generally is the direct degradation of organic substances of hydroxyl free radical reaction by producing behind the uviolizing photocatalyst; or produce the oxygenant degradation of organic substances of hydroxyl radical free radical (OH), ozone one class by electrolytic reaction; it is more thorough that this degradation pathway is decomposed organism; be difficult for producing the murder by poisoning intermediate product; more meet requirement on environmental protection, this method is commonly called organic catalytic oxidation process.So-called catalysis, be meant under electric field action, be present in catalyst surface or electrode surface and the solution modifier in mutually and can promote or be suppressed at the electron-transfer reaction that takes place on the catalyzer, and the class photoelectrochemistry effect that catalyst surface or the solution modifier in mutually itself does not change.
Catalytic electrode material has " hole " effect in electric field, that is to say when reaching the electric field of certain intensity, the valence band electronics can be crossed the forbidden band and enter conduction band, on valence band, form electricity simultaneously and swash the hole, there is the ability of very strong trapped electron in this hole, can capture material surface solvent and organic electronics and redox reaction takes place.In the aqueous solution, just show as water molecules and lose an electronics formation strong oxidizing property free radical hydroxyl.The hydroxyl radical free radical effective active time is short, with chemical substance generation chain reaction after if any residue, hydroxyl decomposes and can be the oxygen G﹠W, the totally nontoxic evil does not produce any detrimental action to surrounding environment.With the microbial process time less than 10s, reaction back organism thoroughly is decomposed into water and carbonic acid gas, is safety and Health equally.Hydroxyl radical free radical, be human know at present have active material most.Hydroxyl has very strong killing action to microorganism, and its concrete effect has: (1) lipid peroxidation; (2) amino-acid oxidase decomposes; (3) protein conformation changes; (4) thymus nucleic acid (DNA) oxidative damage; (5) cytopigment decolouring.The main component of the animals and plants that swim, bacterium, vibrios and spore etc. in the water is: carbohydrate, lipid, protein, nucleic acid and the intravital biochemical reaction of biology is played material-enzyme of catalysis and regulating effect etc.Hydroxyl can be killed biology at a terrific speed to the strong oxidation of microorganism cells.The chemical reaction that hydroxyl radical free radical participates in is to belong to free radical reaction, and chemical reaction velocity is exceedingly fast.The reaction rate constant of the organic substance of C-H, C-C key mostly more than 109L/ (mols), is reached or surpasses rate of diffusion ultimate value [1010L/ (mols)], exceed 7 orders of magnitude again than the reaction rate constant of ozone.Chemical time is less than 1s, biochemical reaction time 1～10s.
The characteristics that flow is big, the treatment time is short are arranged in Ballast water treatment, and can not cause corrosion hull.Especially in electrolytic process, do not allow to produce the gas that chlorine, hydrogen, methane, carbon monoxide etc. are dangerous and poison, and to the strictness of ballast water treatment equipment requirements, the different water surroundings such as water quality of seawater, fresh water, mixing water quality and different turbidity must be able to adapted to, and identical treatment effect will be reached.
The catalysis electrode of development mainly is used in chlor-alkali industry or other electrolysis industries now, or the process field of organic waste water, can not satisfy short period of time, high flow capacity and other requirement of ballast water treatment.Especially existing electrode materials when the Water-Electrolyte environment of low conductivity uses, because the content of catalytic material is little, can not get a desired effect, and therefore can not satisfy the requirement of this complicated water quality environment of processing ballast.
Summary of the invention
Weak point at the prior art existence, technical problem to be solved by this invention is, a kind of multi-dimensional nanomaterial micro-current electron exciting electrode and preparation method thereof is provided, be applied to the ballast water for ship water treatment field, making boats and ships no matter travel at rivers still is that the ballast water treatment system that has this electrode can be used in ocean, satisfy the requirements such as short period of time, high flow capacity of ballast water treatment, guarantee the ballast water treatment effect.
For solving above-mentioned technical problem, the technical scheme that the present invention takes is, a kind of preparation method of multi-dimensional nanomaterial micro-current electron exciting electrode, and it comprises following content:
1, pre-treatment electrode titanium matrix; 2, by the control treatment temp on electrode matrix, turn out anatase octahedrite and rutile mutually ratio be 2: 8～7: 3 nano titanium oxide crystallizing layer; 3, more from the teeth outwards sintering one deck various ingredients, blended metal oxide nano coating are by a certain percentage arranged.
The preparation method of above-mentioned multi-dimensional nanomaterial micro-current electron exciting electrode, it comprises following content:
1, pre-treatment electrode titanium matrix: with 40 orders, 120 orders, 320 order sand paper the titanium matrix is polished successively, make the titanium matrix surface metalluster that is silvery white in color; Alkali cleaning then: with mass percent is that 15～40% sodium hydroxide or potassium hydroxide solution soak the titanium matrix through polishing, and the control bath temperature soaked 2 hours at 80～100 ℃; Pickling again: soak the titanium matrix with any or its mixing solutions of mass percent in 10～25% oxalic acid, hydrochloric acid, sulfuric acid, nitric acid, 80～100 ℃ of control bath temperatures soaked 2 hours; At last that pre-treatment is good titanium matrix be placed on deposit in 5～15% the oxalic acid standby.
2, cultivate the nano titanium oxide crystallizing layer: using plasma vapour deposition process or additive method, film in titanium matrix surface deposition layer of titanium dioxide, the thickness of titanium deoxid film is several to tens nanometers, then in high temperature oven (retort furnace), slowly at the uniform velocity heat up from room temperature, heat-up rate is controlled at 1～3 ℃/min, last controlled temperature is at 500～700 ℃, be incubated 1.5 hours, naturally cooling then, obtain the multi-C stereo structure, anatase octahedrite and rutile mutually ratio be 2: 8～7: 3 nano titanium oxide crystallization bottom.
3, preparation electrode surface oxide coating: on the surface of crystallization nano titanium oxide bottom, pass through the Prepared by Sol Gel Method top coat, concrete grammar is as follows: at first prepare masking liquid, salt or its oxide compound of at least a metallic salt among metal A u, Ag, Pb, Si, Sn, Pt, Ir, Sb, In, Ge, Ru, Rh, Pd, Ta, Zr, Ti and the Os and rare earth material are allocated by certain mole proportioning and the solvent that chooses, be mixed with sol gel solution, as masking liquid, be with or without the salts solution of the Ag that accounts for metal 2 ~ 10% mass percents in this masking liquid; Then on the surface with the titanium dioxide bottom that is coated to electrode of the accurate equal and quantitative of masking liquid, dry postcooling is to room temperature, carry out formula control thermal treatment again, last cooling naturally, above-mentioned coating and formula control thermal treatment want repeated multiple times to carry out, between several times to tens times, the thickness of each coating is at Nano grade.
Described masking liquid can be one or more, and metal ion or rare earth ion in every kind of masking liquid are all incomplete same, and each coating all can be used identical or different masking liquid.
Above-mentioned metallic salt is the muriate or the nitrate of described metal, and wherein iridium is that chloro-iridic acid, platinum are Platinic chloride, and titanium is a tetrabutyl titanate.
Described solvent is selected from one or more in water, ethanol, Virahol, propyl carbinol, Pentyl alcohol, toluene, methyl ether, ether, methane amide, the ethanamide.Solvent should be able to dissolve the salt of selection, simultaneously suitable volatility is arranged again, and does not corrode the titanium matrix.
Described coating and formula control heat treatment process are: after being coated with, be cooled to room temperature dry between 90 ~ 160 ℃ more than 30 minutes with far-infrared lamp at every turn, carry out time variable control thermal treatment then; Described time variable control thermal treatment is: linear temperature increase to 450 ~ 650 ℃ at the uniform velocity are incubated 0.5 ~ 3 hour; Or: the speed with 1 ~ 4 ℃/min is warmed up to 120 ℃ earlier, is incubated 5 ~ 20 minutes, and then is warmed up to 350 ~ 420 ℃ of insulations 30 minutes with the speed of 1 ~ 4 ℃/min, and the speed with 1 ~ 4 ℃/min is warmed up to 450 ~ 650 ℃ at last, is incubated 0.5 ~ 3 hour; Or: the speed with 1 ~ 4 ℃/min is warmed up to 120 ℃ earlier, is incubated 5 ~ 30 minutes, and the speed of last 1 ~ 4 ℃/min is warmed up to 450 ~ 650 ℃, is incubated 0.5 ~ 3 hour; Its last processing that applies of wherein any mode all will be incubated 3 hours.
The preparation method of above-mentioned multi-dimensional nanomaterial micro-current electron exciting electrode, in the middle of its enforcement before the preparation electrode surface oxide coating of completing steps 2 backs, step 3 or in step 3, also have following operation steps: the electrode in the making processes as negative electrode, put into gold ion solution as electrolytical plating tank, electrodeposition is 10 ~ 15 minutes under electric current 0.05 ~ 0.1A/dm2 situation, the several gold atom layers to tens nano thickness of galvanic deposit last layer; After electrodeposition is finished, rinse well repeatedly, dry naturally then or under 100 ℃ situation, dried by the fire 30 minutes with far-infrared lamp with deionized water, naturally cool to room temperature, with the speed of 1 ℃/min linear temperature increase to 300 ~ 600 ℃ at the uniform velocity, be incubated 3 hours then, carry out subsequent operations then.Deposited Au of the present invention middle layer can be also will heat-treat after electrodeposition is finished in bottom or middle layer.
The preparation method of above-mentioned multi-dimensional nanomaterial micro-current electron exciting electrode, the coating method of its top coat uses dip-coating method or squeegee process or spraying method.The present invention advises using squeegee process, uses the wool banister brush, can guarantee homogeneity when brushing like this, and the nanocrystal titanium deoxid film of protection cultivation is not damaged again.
A kind of multi-dimensional nanomaterial micro-current electron exciting electrode with method for preparing, comprise electrode titanium matrix, it is several titanium dioxide crystallizing layers to tens nanometers that its electrode titanium matrix is provided with thickness, and the anatase octahedrite of this crystallizing layer and rutile ratio mutually are 2: 8～7: 3; The nano titanium oxide crystallizing layer also is coated with the metal oxide semiconductor activated coating outward, and this coating is the metal oxide activated coating of multi-level different proportionings.
Above-mentioned multi-dimensional nanomaterial micro-current electron exciting electrode, between its titanium dioxide crystallizing layer and the metal oxide activated coating or metal oxide activated coating inside also deposit the several gold atom layers to tens nano thickness of one deck.
The present invention at first obtains one deck nano-titanium dioxide film at matrix surface by plasma vapor deposition processes or additive method, thickness is greatly about about tens nanometers, control thermal treatment temp then and heat-treat, obtain red schorl phase titanium dioxide and account for 30 ~ 80% nano titanium oxide crystalline membrane (other crystallized forms are anatase octahedrite) in high temperature oven (retort furnace) the inside.Thermal treatment process of the present invention requires heat-up rate slow, allows the titanium dioxide sufficient crystallising, reduces lattice imperfection.Cultivating the nano titanium oxide crystalline membrane that generates at last is 3-D solid structure, has increased the specific surface area of electrode greatly.This step is a committed step of the present invention, and the thickness of titanium dioxide crystalline film and quality have determined the height of electrode catalyst effect.The present invention tested simultaneously and vacuumized or the nitrogen protection thermal treatment process, obtained the unsaturated nano titanium oxide crystalline membrane of oxygen, and better effects if is high especially but technology controlling and process requires.Usually with muriate or nitrate, iridium platinum is generally used chloro-iridic acid, Platinic chloride to metallic salt, and titanium is generally used tetrabutyl titanate.Choice of Solvent is wanted to dissolve the salt of selecting, and simultaneously suitable volatility is arranged again, does not corrode the titanium matrix, general used water, ethanol, Virahol, propyl carbinol, Pentyl alcohol, toluene, methyl ether, ether, methane amide, ethanamide etc.By correlation step, make sol gel solution, accurately be coated in uniformly on the battery lead plate, dry under suitable temperature, enter then in the programmable high temperature sintering case, carry out formula control thermal treatment, last cooling naturally.But apply and heat treatment process as required repeated multiple times carry out (greatly about several times to tens times, the solution amount that each strict control applies guarantees the homogeneity of coating, and guarantees that the thickness of each coating will be at Nano grade).Guarantee the quality of electrode surface oxide coating.
Use the multi-dimensional nanomaterial micro-current electron exciting electrode of electrode preparation method preparation of the present invention, its top coat is to be coated in rutile to account for mutually on the surface of a certain proportion of mixing nano titanium oxide crystallization bottom, it is the stereo multi-dimensinal structure, the electrode specific surface area of preparation is big, the catalytic activity height, good conductivity.Electrode of the present invention is no matter still can both produce a large amount of hydroxyl radical free radical (OH), peroxy radical (O at fresh water in seawater, salt solution
2), H
2O
2, strong oxidizer with high activity such as ozone, hypochlorous acid, produce the advanced oxidation reflection with organism, microorganism, bacterium in the water etc., by dehydrogenation, electrophilic and transfer transport effect, form the activatory organic free radical, produce the combustion-type chain reaction, make the degraded fully rapidly of organism, microorganism, bacterium, can realize organic wide spectrum, non-selectivity oxidative degradation are killed, the big flow of ballast water treatment, the characteristic of short period of time can be satisfied, the high request of ballast water treatment quality can be satisfied again.Electrode of the present invention also is applicable to water treatment and field of environment protection, is used for killing organic microbial that water contains, bacterium etc.
Embodiment
Embodiment one
1, the pre-treatment of titanium matrix:
Polishing: with 40 orders, 120 orders, 320 order sand paper the titanium matrix is polished successively, make the titanium matrix surface metalluster that is silvery white in color.
Alkali cleaning: with mass percent is that 15 ~ 40% sodium hydroxide or potassium hydroxide solution soak the titanium matrix through polishing, and the control bath temperature soaked 2 hours at 80 ~ 100 ℃.
Pickling: soak the titanium matrix with any or its mixing solutions of mass percent in 10 ~ 25% oxalic acid, hydrochloric acid, sulfuric acid, nitric acid, 80 ~ 100 ℃ of control bath temperatures soaked 2 hours.
The titanium matrix that pre-treatment is good be placed on deposit in 5 ~ 15% the oxalic acid standby.
2, cultivate red schorl phase titanium dioxide and account for a certain proportion of mixing nano titanium oxide crystallization bottom:
The using plasma vapour deposition process, film in titanium matrix surface deposition layer of titanium dioxide, control titanium dioxide thickness several to tens nanometers, then in high temperature oven (retort furnace), slowly at the uniform velocity heat up from room temperature, heat-up rate is controlled at 1 ~ 3 ℃/min, last controlled temperature is at 500 ~ 700 ℃, be incubated 1.5 hours, naturally cooling then, obtain the multi-C stereo structure, anatase octahedrite and rutile mutually ratio be 2: 8,3: 7,4: 6,5: 5,6: 4,7: 3 nano titanium oxide crystallization bottom.
3, preparation sol gel solution and brushing and thermal treatment:
The muriate or the nitrate solution of the semiconductor material of 0.2 ~ 1.0mol/l of difference preparing metal Pb, Si, Sn, Sb, In, Ge, Ru, Rh, Pd, Ta, Zr, Ti and Os, solvent is water or organic solvents such as ethanol, propyl carbinol; Chloro-iridic acid, platinum acid chloride solution and the tetrabutyl titanate solution of preparation 0.2 ~ 0.5mol/l.The concentrated hydrochloric acid hydrotropy that adds 3 ~ 10ml as required.Choose one or more solution as required and be mixed with sol solutions, one group of sol solutions can preparing the different proportionings of different metal uses, the characteristics of present embodiment electrode are exactly that the material of the metal oxide semiconductor from the bottom to the top layer is different with proportioning, reach different purposes with this.
In the present embodiment, at first prepare two or more the solution among In, Sn, Sb, Ge, the Ti, wherein In accounts for 10 ~ 65%, add the earth solution that accounts for 0.5 ~ 6% mass percent, make sol gel solution, strictness quantitatively is brushed on the electrode surface, the repeated multiple times brushing.After being coated with, dry more than 30 minutes between 90 ~ 160 ℃, be cooled to room temperature with far-infrared lamp at every turn; Put into high temperature oven then and carry out time variable control thermal treatment.The time variable control heat treatment process that the present invention says comprises: 1, linear temperature increase to 450 ~ 650 ℃ at the uniform velocity are incubated 0.5 ~ 3 hour; 2, elder generation is warmed up to 120 ℃ with the speed of 1 ~ 4 ℃/min, is incubated 5 ~ 20 minutes, and then is warmed up to 350 ~ 420 ℃ of insulations 30 minutes with the speed of 1 ~ 4 ℃/min, and the speed with 1 ~ 4 ℃/min is warmed up to 450 ~ 650 ℃ at last, is incubated 0.5 ~ 3 hour; 3, elder generation is warmed up to 120 ℃ with the speed of 1 ~ 4 ℃/min, is incubated 5 ~ 30 minutes, and the speed of last 1 ~ 4 ℃/min is warmed up to 450 ~ 650 ℃, is incubated 0.5 ~ 3 hour.Notice that the pyroprocessing of last brushing requires insulation 3 hours.
Prepare two or more the solution of In, Ge, Ru, Sb, Rh, Pd, Ta, Sn then, add the earth solution that accounts for 0.5 ~ 6% mass percent, make sol gel solution, strictness quantitatively is brushed on the electrode surface, the repeated multiple times brushing.After being coated with, dry more than 30 minutes between 90 ~ 120 ℃, be cooled to room temperature with far-infrared lamp at every turn; Put into high temperature oven then and carry out time variable control thermal treatment.The same step of time variable control heat treatment process that this step is said.
Prepare two or more solution of In, Ge, Ru, Sb, Rh, Pd, Ta, Ir, Pt, Os at last, add the earth solution that accounts for 0.5 ~ 6% mass percent, make sol gel solution, strictness quantitatively is brushed on the electrode surface, the repeated multiple times brushing.After being coated with, dry more than 30 minutes between 90 ~ 120 ℃, be cooled to room temperature with far-infrared lamp at every turn; Put into high temperature oven then and carry out time variable control thermal treatment.The time variable control heat treatment process that this step is said is with 1 ~ 3 ℃/min linear temperature increase to 450 ~ 600 ℃ at the uniform velocity, is incubated 1 ~ 3 hour.The heat treatment process of last brushing is with 1 ℃/min linear temperature increase to 500 ~ 600 ℃ at the uniform velocity, is incubated 3 hours.
After below heat treatment process finishes each time, all room temperature to be naturally cooled to, just next step brushing can be carried out then.
Embodiment two
Present embodiment and embodiment one different place is, before step 3 or in the middle of the enforcement of step 3, adds following single stepping, and concrete operations are:
The electrode in the making processes as negative electrode, put into gold ion solution as electrolytical plating tank, electrodeposition is 10 ~ 15 minutes under electric current 0.05 ~ 0.1A/dm2 situation, and galvanic deposit last layer metallic gold can obtain several gold atom layers to tens nano thickness like this.After electrodeposition is finished, rinse well repeatedly, dry naturally then or under 100 ℃ situation, dried by the fire 30 minutes, cool to room temperature naturally, with the speed of 1 ℃/min linear temperature increase to 300 ~ 600 ℃ at the uniform velocity, be incubated 3 hours then with far-infrared lamp with deionized water.
The catalysis electrode that present embodiment obtains, catalytic performance is better than the catalysis electrode of embodiment one, under the same current density situation, reduces electrolysis voltage, cuts down the consumption of energy, and improves current efficiency.
Embodiment three:
1, the pre-treatment of titanium matrix: with embodiment one.
2, cultivate red schorl phase titanium dioxide and account for a certain proportion of mixing nano titanium oxide crystallization bottom:
The using plasma vapour deposition process, film in titanium matrix surface deposition layer of titanium dioxide, control titanium dioxide thickness several to tens nanometers, then in high temperature oven (retort furnace), slowly at the uniform velocity heat up from room temperature, heat-up rate is controlled at 1 ~ 3 ℃/min, last controlled temperature is at 500 ~ 700 ℃, be incubated 1.5 hours, naturally cooling then, obtain the multi-C stereo structure, anatase octahedrite and rutile mutually ratio be 2: 8,3: 7,4: 6,5: 5,6: 4,7: 3. nano titanium oxide crystallization bottom.
3, preparation sol gel solution and brushing and thermal treatment
The muriate or the nitrate solution of the semiconductor material of 0.2 ~ 1.0mol/l of preparation Ag, Pb, Si, Sn, Sb, In, Ge, Ru, Rh, Pd, Ta, Zr, Ti and Os, solvent can be water or organic solvents such as ethanol, propyl carbinol; Chloro-iridic acid or the platinum acid chloride solution of preparation 0.2 ~ 0.5mol/l; Preparation tetrabutyl titanate solution.The hydrochloric acid hydrotropy that can add 3 ~ 10ml as required.Choose one or more solution as required and be mixed with sol solutions, the combination solution that can prepare the different proportionings of different metal uses, the characteristics of electrode of the present invention are exactly that the material of the metal oxide semiconductor from the bottom to the top layer is different with proportioning, reach different purposes with this.
At first prepare two or more solution of In, Sn, Sb, Ge, Ti, wherein In accounts for 10 ~ 65%, adds the earth solution that accounts for the 0.5-6% mass percent, makes sol gel solution, and strictness quantitatively is brushed on the electrode surface, the repeated multiple times brushing.After being coated with, dry more than 30 minutes between 90 ~ 160 ℃, be cooled to room temperature with far-infrared lamp at every turn; Put into high temperature oven then and carry out time variable control thermal treatment.The time variable control heat treatment process that the present invention says comprises: 1, linear temperature increase to 450 ~ 650 ℃ at the uniform velocity are incubated 0.5 ~ 3 hour; 2, elder generation is warmed up to 120 ℃ with the speed of 1 ~ 4 ℃/min, is incubated 5 ~ 20 minutes, and then is warmed up to 350 ~ 420 ℃ of insulations 30 minutes with the speed of 1 ~ 4 ℃/min, and the speed of last 1 ~ 4 ℃/min is warmed up to 450 ~ 650 ℃, is incubated 0.5 ~ 3 hour; 3, elder generation is warmed up to 120 ℃ with the speed of 1 ~ 4 ℃/min, is incubated 5 ~ 30 minutes, and the speed of last 1 ~ 4 ℃/min is warmed up to 450 ~ 650 ℃, is incubated 0.5 ~ 3 hour.Notice that the pyroprocessing of last brushing requires insulation 3 hours.
Prepare two or more the solution of In, Ge, Ru, Sb, Rh, Pd, Ta, Sn then, add the earth solution that accounts for 0.5 ~ 6% mass percent, add the Ag+ solution that accounts for 2 ~ 10% mass percents, make sol gel solution, strictness quantitatively is brushed on the electrode surface, the repeated multiple times brushing.After being coated with, dry more than 30 minutes between 90 ~ 120 ℃, be cooled to room temperature with far-infrared lamp at every turn; Put into high temperature oven then and carry out time variable control thermal treatment.The same step of time variable control heat treatment process that this step is said.
Prepare two or more solution of In, Ge, Ru, Sb, Rh, Pd, Ta, Ir, Pt, Os at last, add the earth solution that accounts for 0.5 ~ 6% mass percent, make sol gel solution, strictness quantitatively is brushed on the electrode surface, the repeated multiple times brushing.After being coated with, dry more than 30 minutes between 90 ~ 120 ℃, be cooled to room temperature with far-infrared lamp at every turn; Put into high temperature oven then and carry out time variable control thermal treatment.The time variable control heat treatment process that this step is said is with 1 ~ 3 ℃/min linear temperature increase to 450 ~ 600 ℃ at the uniform velocity, is incubated 1 ~ 3 hour.The heat treatment process of last brushing is with 1 ℃/min linear temperature increase to 500 ~ 600 ℃ at the uniform velocity, is incubated 3 hours.
After below heat treatment process finishes each time, all room temperature to be naturally cooled to, just next step brushing can be carried out then.
Silver-colored Ag has been introduced in the present embodiment the inside, because silver self has very strong sterilizing ability, the introducing of silver has strengthened the ability of killing of electrode pair aquatic organic matter and bacterium, and the introducing of silver has simultaneously also improved the catalytic activity of electrode.The introducing of silver is not limited at the second layer among the present invention, also can introduce in the first layer or the 3rd layer, perhaps two-layer therein or three layers all introduce, equally in protection scope of the present invention.
Embodiment four
Present embodiment and embodiment three different places are, before step 3 or in the middle of the enforcement of step 3, add following single stepping, and concrete operations are:
The electrode in the making processes as negative electrode, put into gold ion solution as electrolytical plating tank, electrodeposition is 10 ~ 15 minutes under electric current 0.05 ~ 0.1A/dm2 situation, and galvanic deposit last layer metallic gold can obtain several gold atom layers to tens nano thickness like this.After electrodeposition is finished, rinse well repeatedly, dry naturally then or under 100 ℃ situation, dried by the fire 30 minutes, cool to room temperature naturally, with the speed of 1 ℃/min linear temperature increase to 300 ~ 600 ℃ at the uniform velocity, be incubated 3 hours then with far-infrared lamp with deionized water.
The electrode that the manner obtains, catalytic activity is better than the electrode of mode three, under the same current density situation, reduces electrolysis voltage, cuts down the consumption of energy, and improves current efficiency.
Form electrolyzer with the electrode for preparing in the foregoing description, according to the requirement of International Maritime meeting (IMO), entrust professional institution, seawater and salt solution are carried out the electrolysis treatment experiment, experimental result is as follows:
One. use this catalysis electrode to handle the experimental result of following two kinds of different water quality:
| Salinity (Salinity) | ??DOC | ??POC | ??TSS | |
| Seawater (Seawater test) | ??＞32PSU | ??＞1mg/l | ??＞1mg/l | ??＞1mg/l |
| Salt water (Brackish water test) | ??3-32PSU | ??＞5mg/l | ??＞5mg/l | ??＞50mg/l |
Two. the initial value of microorganism in the data representation test water in the form.
The part that highlights in the above form is represented up to standard fully.
Three. the concentration of seawater tank deck gas:
Four. the concentration of salt water tank deck gas
Five. chemical substance in the raw water quality and situation up to standard:
(1) seawater raw water quality (mean value of three parallel samples and standard error)
The part that highlights in the above form is represented up to standard fully.
(2) salt water raw water quality (mean value of three parallel samples and standard error)
The part that highlights in the above form is represented up to standard fully.
By last table (1), (2) as seen, in seawater and salt water experiment, former water TSS, DOC, POC are up to standard.
Six. the temperature of former water before handling, salinity, dissolved oxygen concentration, the temperature of water after treatment and contrast water sample, salinity, dissolved oxygen concentration.
Seven. former water, treated water, the total residual chlorine (representing) of contrast water sample with total chlorine and free chlorine, numerical value is the mean value of three parallel samples.
Eight. DBP in the seawater (disinfection byproduct (DBP)) content.Sampling in the time of the 5th day is not through handling.
Nine. DBP in the salt water (disinfection byproduct (DBP)) content.Sampling in the time of the 5th day is not through handling.
Ten. after just having stored through processing and through 5 days, 10 to 50 microns biological content
The part that highlights in the above form is represented up to standard fully.
11. water after just having stored through processing and through 5 days and the heterotrophic bacterium in the contrast sample, intestinal bacteria kill vibrios, the content of enterococcus bacteria
The part that highlights in the above form is represented up to standard fully.
Claims (10)
1. the preparation method of a multi-dimensional nanomaterial micro-current electron exciting electrode, it comprises following content:
A, pre-treatment electrode titanium matrix; B, by the control treatment temp on electrode matrix, turn out anatase octahedrite and rutile mutually ratio be 2: 8～7: 3 nano titanium oxide crystallizing layer; C, sintering one deck has various ingredients, blended metal oxide nano coating by a certain percentage on the titanium dioxide crystallizing layer surface of electrode.
2. the preparation method of multi-dimensional nanomaterial micro-current electron exciting electrode according to claim 1, it comprises following content:
A, pre-treatment electrode titanium matrix: with 40 orders, 120 orders, 320 order sand paper the titanium matrix is polished successively, make the titanium matrix surface metalluster that is silvery white in color; Alkali cleaning then: with mass percent is that 15～40% sodium hydroxide or potassium hydroxide solution soak the titanium matrix through polishing, and the control bath temperature soaked 2 hours at 80～100 ℃; Pickling again: soak the titanium matrix with any or its mixing solutions of mass percent in 10～25% oxalic acid, hydrochloric acid, sulfuric acid, nitric acid, 80～100 ℃ of control bath temperatures soaked 2 hours; At last that pre-treatment is good titanium matrix be placed on deposit in 5～15% the oxalic acid standby;
B, cultivation nano titanium oxide crystallizing layer: using plasma vapour deposition process or additive method, film in titanium matrix surface deposition layer of titanium dioxide, the thickness of titanium deoxid film is several to tens nanometers, then in high temperature oven (retort furnace), slowly at the uniform velocity heat up from room temperature, heat-up rate is controlled at 1～3 ℃/min, last controlled temperature is at 500～700 ℃, be incubated 1.5 hours, naturally cooling then, obtain the multi-C stereo structure, anatase octahedrite and rutile mutually ratio be 2: 8～7: 3 nano titanium oxide crystallization bottom;
C, preparation electrode surface oxide coating: on the surface of crystallization nano titanium oxide bottom, pass through the Prepared by Sol Gel Method top coat, concrete grammar is as follows: at first prepare masking liquid, salt or its oxide compound of at least a metallic salt among metal A u, Ag, Pb, Si, Sn, Pt, Ir, Sb, In, Ge, Ru, Rh, Pd, Ta, Zr, Ti and the Os and rare earth material are allocated by certain mole proportioning and the solvent that chooses, be mixed with sol gel solution, as masking liquid, be with or without the salts solution of the Ag that accounts for metal 2 ~ 10% mass percents in this masking liquid; Then on the surface with the titanium dioxide bottom that is coated to electrode of the accurate equal and quantitative of masking liquid, dry postcooling is to room temperature, carry out formula control thermal treatment again, last cooling naturally, above-mentioned coating and formula control thermal treatment want repeated multiple times to carry out, between several times to tens times, the thickness of each coating is at Nano grade.
3. the preparation method of multi-dimensional nanomaterial micro-current electron exciting electrode according to claim 2, its described masking liquid can be one or more, metal ion or rare earth ion in every kind of masking liquid are all incomplete same, and each coating all can be used identical or different masking liquid.
4. the preparation method of multi-dimensional nanomaterial micro-current electron exciting electrode according to claim 3, its described metallic salt is the muriate or the nitrate of described metal except that iridium, platinum, titanium; Wherein iridium is that chloro-iridic acid, platinum are Platinic chloride, and titanium is a tetrabutyl titanate.
5. the preparation method of multi-dimensional nanomaterial micro-current electron exciting electrode according to claim 4, its described solvent is selected from one or more in water, ethanol, Virahol, propyl carbinol, Pentyl alcohol, toluene, methyl ether, ether, methane amide, the ethanamide.
6. the preparation method of multi-dimensional nanomaterial micro-current electron exciting electrode according to claim 5, its described coating and formula control heat treatment process are: after being coated with at every turn, be cooled to room temperature dry between 90 ~ 160 ℃ more than 30 minutes with far-infrared lamp, carry out time variable control thermal treatment then; Described time variable control thermal treatment is: linear temperature increase to 450 ~ 650 ℃ at the uniform velocity are incubated 0.5 ~ 3 hour; Or: the speed with 1 ~ 4 ℃/min is warmed up to 120 ℃ earlier, is incubated 5 ~ 20 minutes, and then is warmed up to 350 ~ 420 ℃ of insulations 30 minutes with the speed of 1 ~ 4 ℃/min, and the speed with 1 ~ 4 ℃/min is warmed up to 450 ~ 650 ℃ at last, is incubated 0.5 ~ 3 hour; Or: the speed with 1 ~ 4 ℃/min is warmed up to 120 ℃ earlier, is incubated 5 ~ 30 minutes, and the speed of last 1 ~ 4 ℃/min is warmed up to 450 ~ 650 ℃, is incubated 0.5 ~ 3 hour; Its last processing that applies of wherein any mode all will be incubated 3 hours.
7. the preparation method of multi-dimensional nanomaterial micro-current electron exciting electrode according to claim 6, it is before the preparation electrode surface oxide coating behind the completing steps 2, in step 3 or in the middle of the enforcement in step 3, also have following operation steps: the electrode in the making processes as negative electrode, put into gold ion solution as electrolytical plating tank, electrodeposition is 10 ~ 15 minutes under electric current 0.05 ~ 0.1A/dm2 situation, the several gold atom layers to tens nano thickness of galvanic deposit last layer; After electrodeposition is finished, rinse well repeatedly, dry naturally then or under 100 ℃ situation, dried by the fire 30 minutes with far-infrared lamp with deionized water, naturally cool to room temperature, with the speed of 1 ℃/mi n linear temperature increase to 300 ~ 600 ℃ at the uniform velocity, be incubated 3 hours then, carry out subsequent operations then.
8. the preparation method of multi-dimensional nanomaterial micro-current electron exciting electrode according to claim 7, the coating method of its top coat uses dip-coating method or squeegee process or spraying method.
9. multi-dimensional nanomaterial micro-current electron exciting electrode with each described preparation method preparation of claim 1 to 8, comprise electrode titanium matrix, it is characterized in that: it is several titanium dioxide crystallizing layers to tens nanometers that its electrode titanium matrix is provided with thickness, and the anatase octahedrite of this crystallizing layer and rutile ratio mutually are 2: 8～7: 3; The nano titanium oxide crystallizing layer also is coated with the metal oxide semiconductor activated coating outward, and this coating is the metal oxide activated coating of multi-level different proportionings.
10. electrode according to claim 9 is characterized in that: also deposit the several gold atom layers to tens nano thickness of one deck between described metal oxide activated coating inner or itself and the titanium dioxide crystallizing layer.
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| CN103288181A (en) * | 2012-02-26 | 2013-09-11 | 桂雷珠 | Thermionic emission type anion water and ozone generator |
| CN103288181B (en) * | 2012-02-26 | 2016-05-25 | 桂雷珠 | Thermal electron emission type anion water and ozone generator |
| CN103551017A (en) * | 2013-10-22 | 2014-02-05 | 上海海事大学 | Conductive catalytic electrode for direct current corona discharge gas purifier and preparation method thereof |
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| CN109594066A (en) * | 2018-12-18 | 2019-04-09 | 福建浩达智能科技股份有限公司 | A kind of preparation method of the super nanocrystalline titanium anode coating of hyperoxia |
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