CN102505127A - Preparation method for noble metal modified titanium anode materials - Google Patents
Preparation method for noble metal modified titanium anode materials Download PDFInfo
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- CN102505127A CN102505127A CN2011104517704A CN201110451770A CN102505127A CN 102505127 A CN102505127 A CN 102505127A CN 2011104517704 A CN2011104517704 A CN 2011104517704A CN 201110451770 A CN201110451770 A CN 201110451770A CN 102505127 A CN102505127 A CN 102505127A
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Abstract
The invention relates to a preparation method for noble metal modified titanium anode materials, belonging to the technical field of high-performance electrode materials. The preparation method for noble metal modified titanium anode materials comprises the following steps of: taking noble metal organic complex as a precursor; atomizing the precursor into atomizing flow after being dissolved in organic solvent; depositing the precursor on the surface of a titanium sheet; thermally decomposing and cooling under the existence of inertia gas; repeating three continuous steps of depositing, thermally decomposing and cooling for at least once; and carrying out aftertreatment, so as to obtain the noble metal modified titanium anode materials. The titanium anode prepared by the method has high yield and less surface exposed point; the noble metal and pure titanium base material have high binding force; and the whole coating has better homogeneity and uniformity. Experiments show that the titanium anode prepared by the method has better electrochemical performance and long service life.
Description
Technical field
The invention belongs to the high performance electrode material technical field, particularly the preparation method of modified with noble metals titanium anode material.
Background technology
The titanium anode plate material is to be able to a large amount of insoluble anode materials that use in the electrochemical industry; Also be referred to as the dimensional stability anode; Be DSA (dimensionally stable anode); It is matrix with the metal titanium, and surface applied is the activated coating of main ingredient with precious metal organic coordination compound or precious metal material, is a kind of new and effective electrode materials that grows up late 1960s.The titanium anode is used for chlorine industry the earliest, has been widely used in the fields such as chemical industry, metallurgy, plating, water treatment, environmental protection, ocean, galvanic protection at present.
1, chlorine industry is used the titanium anode
Chlorine industry is used for chlorine industry early than nineteen sixty-eight by Italian DeNora company with titanium anode titanium electrode and produces.At present, China's caustic soda overall throughput is 730 * 104t (1998), and several countries such as the U.S. are 3000 * 104t, basically all uses titanium anode electricity groove.Every of homemade 30 type titanium anodes electricity groove needs with titanium material 210kg; The chlorine industry titanium electrode used in the whole world just consumes the about 1.54 * 104t of titanium material like this; It is an effective way of applying the titanium material; The deep processing that precious metal surface modification simultaneously can effectively promote the metal titanium material is worth, and can realize big production capacity and high profit.
2, used for non-ferrous metal titanium anode sun is extracted in galvanic deposit
Electrolytic metallurgy has occupied very big proportion in hydrometallurgy industry.Adopt the non-ferrous metal of electrolytic metallurgy production Zn to be arranged, Cd, Cu, Mn, Co, Cr etc.It is to select suitable anode material for use that the metal greatest difficulty is extracted in galvanic deposit.Antianode will aspire for stability, anti-corrosion, but life-time service, the antianode process has good electro catalytic activity, to reduce the overpotential and the bath voltage of anodic reaction.The widely-used coated titanium electrode of metal industry is extracted in galvanic deposit in the last few years, and along with hydrometallurgical technology becomes mainstream technology, precious metal surface modified titanium anodes panel material will become the critical material in this field.
3, electrolysis legal system ionized water (alkaline ion water and acid electrolyzed functional water) titanium anode
Anode, the negative electrode of the ionic water generator in past are all used the titanium platinized electrode both at home and abroad.The titanium platinized electrode costs an arm and a leg.Adopt precious metal surface modified titanium anodes panel material, can make electrolyzer be in high bath voltage 30V operation down, output fine alkaline ion water and acid electrolyzed functional water, various aspects of performance can be compared with the titanium platinized electrode.And precious metal surface modified titanium anodes panel material is cheap, after helping domesticizing.
4, the titanium anode is used in water treatment
In the processing of process water, factory's treatment of cyanide waste water is electroplated in the processing of hospital sewage; And all to adopt high performance titanium anode material in the processing of power station cooling circulating water, and adopt precious metal surface modified titanium anodes panel material purifying treatment effectively, make scale inhibition performance greater than 94%; Descaling rate is more than or equal to 94%; Sterilizing rate is greater than 97%, and algaecidal rate 100% meets sewage drainage standard fully.
The following several method of the general employing of titanium anode plate material prepn:
(1) thermolysis technology of preparing
Precursor is dissolved in the suitable solvent and forms solution, and solution is coated on the pretreated titanium matrix, and solvent evaporation in 350～450 ℃ of decomposition, forms the title complex layer of several micron thick on metallic titanium matrix.In thermal decomposition process, the metallic titanium matrix surface is formed the thin TiOx of one deck by partially oxidation, has isolated being connected of matrix metal and coated material; Increase plate resistance; Have influence on the electrochemical behavior and the service life of title complex layer, coated component and masking liquid proportioning are inconsistent simultaneously, cause the coating structure composition profiles inhomogeneous; Be partial coating title complex particle hypertrophy, limited the exploitation of high performance anode material.
(2) sol-gel method (sol-gel)
The Japan scholar adopts the sol-gel method to prepare ultra-fine RuO
2-TiO
2And RuO
2-TiO
2-SnO
2The titanium anode material adopts this technology can develop nanostructure titanium anode material, improves anode activity and corrosion resistance nature.But adopt the sol-gel method to need can generate anatase titanium oxide at 400 ℃ of following sintering, the rapid deterioration anode performance also unavoidably causes body to worsen.From raw material, because of the sol-gel method need adopt metal alkoxide as precursor, and the synthetic difficulty of precious metal alkoxide is big, and chemical property is active, is easy to hydrolytic precipitation, thereby causes the sol-gel method to receive bigger restriction in force.
(3) Pechini preparation technology
Adopt solution polymerization process, under the effect of polyhydroxy-alcohol, organic acid and metals ion form inner complex, and inner complex is polyesterification in heat-processed, forms by the equally distributed vibrin of stoichiometric ratio, and at high temperature obtains precious metal organic coordination compound coating.
In recent years; Anode preparation method is along with the employing of novel process and new technology; Some new preparation technologies have been developed again; As: electromagnetic induction heating method (electromagnetic induction heating) adopts electromagnetic induction heating that precursor is decomposed fast and reduce the matrix oxidation, but length consuming time needs 3～10 hours.The LASER HEATING method adopts CO
2Laser apparatus can shorten heat-up time greatly as pyrotoxin, greatly weakens the oxidation of matrix, but the entire operation process control parameter is more, complicated operation, difficult quality control.
Still there are many shortcomings in the titanium anode plate material at present, is improving the active while as adopting high reactivity prescription coating, and the anode material life-span reduces greatly, and strengthening electrode life is about 10 hours; The precious metal element consumption is big for another example, causes the anode material cost too high; Be bonding force sharply decay under complicated electric field, harsh working condition of noble coatings and titanium base material at last, cause coating shedding, the base material corrosion.Based on above problem, must improve in the preparation technology of titanium anode plate material.
Summary of the invention
Technical problem to be solved by this invention is to improve the bonding force of noble coatings and titanium base material, makes that the catalytic activity of titanium anode material improves, the growth in work-ing life.
The preparation method of modified with noble metals titanium anode material; Adopt the precious metal organic coordination compound as presoma; Presoma is atomized into atomization air flow after being dissolved in organic solvent, is deposited on titanium metal sheet material surface, and has thermolysis down, cooling in rare gas element; Deposition, thermolysis, three successive steps of cooling are repeated more than 1 time, and aftertreatment promptly gets.
The precious metal organic coordination compound is the title complex that precious metal and organic cpds chelating form.Said precious metal is the platinum metals;
base, promptly organic cpds is a methyl ethyl diketone.
The selection of said presoma precious metal organic coordination compound is the different performance requirement according to the titanium anode material, can select for use single a kind of precious metal organic coordination compound to make unit modified with noble metals titanium anode material; Or the mixture formed of the precious metal organic coordination compound of selecting two or more different precious metals for use.
Most preferred, said precious metal organic coordination compound is at least a in methyl ethyl diketone platinum, methyl ethyl diketone ruthenium, methyl ethyl diketone rhodium, methyl ethyl diketone iridium, the palladium acetylacetonate.
Said organic solvent is at least a in absolute ethyl alcohol, toluene, the DMSO 99.8MIN..
Said rare gas element is at least a in nitrogen, the argon gas.
Temperature is controlled at 65～80 ℃ during said deposition.
Said thermolysis is that the precious metal organic coordination compound resolves into precious metal and organic cpds under its heat decomposition temperature, decomposes the back noble metal loading in the titanium anode, and organic cpds vapors away.When the precious metal organic coordination compound was at least a in methyl ethyl diketone platinum, methyl ethyl diketone ruthenium, methyl ethyl diketone rhodium, methyl ethyl diketone iridium, the palladium acetylacetonate, heat decomposition temperature was 220～400 ℃ of 20～100min down.
The said naturally cooling that is cooled to.
Said aftertreatment is that the titanium anode material was in 380～410 ℃ of heating 50～70 minutes.
Atomization air flow when deposition is carrier gas with the rare gas element, and carrier gas air pressure remains on 0.1～0.2MPa.
For the precious metal thickness that makes the titanium anode material reaches desired thickness (being generally about 20 microns); And precious metal is evenly distributed; Can deposition, thermal decomposition steps be repeated for several times, every deposition once needs to deposit after the thermolysis next time again; The titanium metal sheet material that has promptly deposited a less noble metal organic coordination compound atomization air flow carries out thermolysis, in atomization air flow, deposits once more after the thermolysis.Preferred deposition, when two successive steps of thermolysis repeat 2～8 times, precious metal is evenly distributed, and thickness is suitable.Most preferably be repetition 3～5 times.
Further; The preparation method of modified with noble metals titanium anode material specifically comprises the deposition of titanium metal pre-treatment, precious metal organic coordination compound, the thermolysis of precious metal organic coordination compound and the post-processing step of titanium anode material, and wherein deposition, two successive steps of thermolysis repeat more than 1 time:
1) deposition of precious metal organic coordination compound:
With the rare gas element is that carrier gas is deposited on the titanium metal substrates surface with precious metal organic coordination compound atomization air flow, depositing time 10～20min, and temperature is controlled at 65～80 ℃ during deposition;
2) thermolysis of precious metal organic coordination compound:
The post-depositional titanium metal substrates of step 1) is placed the thermolysis of inert atmosphere stove, naturally cooling;
3) aftertreatment of titanium anode material:
With step 2) titanium anode material after the thermolysis promptly got in 380～410 ℃ of heating in 50～70 minutes.
Further,
Step 1) carrier gas air pressure remains on 0.1～0.2MPa.Depositing time is preferably 14～20min.
Step 1) precious metal organic coordination compound is dissolved in the diluting soln that organic solvent is made into 3～8wt%, is atomized into precious metal organic coordination compound atomization air flow then.
Step 2) thermal decomposition steps can make precious metal and metal titanium base material mortise.
The step 3) aftertreatment is preferably 385～405 ℃ of heating 55～65 minutes.
When the precious metal organic coordination compound is at least a in methyl ethyl diketone platinum, methyl ethyl diketone ruthenium, methyl ethyl diketone rhodium, methyl ethyl diketone iridium, the palladium acetylacetonate:
Step 2) when the precious metal organic coordination compound be single precious metal organic coordination compound when (only containing a kind of precious metal), post-depositional metal titanium base material placed 250～400 ℃ of inert atmosphere stove pyrolysis 20～100 minutes.
Step 2) when the precious metal organic coordination compound be that binary precious metal organic coordination compound is when (containing two kinds of precious metals); When particularly binary precious metal organic coordination compound is methyl ethyl diketone iridium and methyl ethyl diketone ruthenium; Post-depositional metal titanium base material places inert atmosphere stove pyrolysis; Pyrolysis divides two sections to carry out, 250～350 ℃ of reactions of low-temperature zone 20～45 minutes, 350～400 ℃ of reactions 20～50 minutes.
Post-processing step can make that titanium anode material profile pattern is high, highly polished, foreign matter content is few.After aftertreatment is accomplished on the titanium anode material precious metal thickness preferably reach more than 20 microns, the titanium anode electrical property that the too thin meeting of precious metal thickness causes processing is relatively poor.
Further, ordinary method is adopted in said titanium metal sheet material pre-treatment, such as: methods such as sandblast polishing, alkali cleaning oil removing, ultrasonic acid etching activation, the titanium after the processing belong to the base material low-temperature vacuum drying and preserve.
Described alkali cleaning oil removing is soaked for using inorganic alkali solution, and the NaOH solution that is preferably weight percent concentration 3～7% soaked 10～30 minutes in 60～80 ℃.
Described ultrasonic acid etching activation is the oxalic acid that titanium metal substrates is placed 10～20% concentration of volume percent, ultrasonic frequency 30～120kHz, ultrasonic power 20～2000W, 60～100 ℃ of ultrasonic activation temperature, 30～80 minutes ultrasonic activation time.
Beneficial effect of the present invention is:
1, adopt ultrasonic acid etching activating technology that pure titanium substrate surface is carried out activation treatment, ultransonic assist measure has effectively improved activation etching efficient, has reduced acid consumption, has reduced pure titanium consumption;
2, precious metal organic coordination compound presoma organic solution surface tension is big, and volatilization temperature is low, and heat decomposition temperature is low, is easy to ultrasonic atomizatio, can efficiently adsorb in surface of metal titanium, and the volatile quantity of precious metal reduces, and effectively reduces noble metal dosage;
3, reduce the heat decomposition temperature of noble metal precursor body, improve the bonding force of precious metal and pure titanium base material, thermal decomposition product is CO
2, non-NO and cl cpd meet the green technology demand for development.
4, atomization technique and traditional brushing technology have tangible difference, reduce noble metal dosage greatly, and can improve yield rate greatly, prevent surperficial dew point, improve the homogeneity and the consistence of whole coating.
The inventive method compared with prior art, pure titanium consumption is little, precious metal and pure titanium base material bonding force are strong, the precious metal consumption is little, thermal decomposition product is CO
2, non-NO and cl cpd, technology is terse, cost is low, pollution-free, is a much progress of green technology, meets the requirement of environmental protection production technique.The anode material chemical property that makes is good, long service life.
Description of drawings
Fig. 1 is embodiment 1 preparation titanium anode surface microcosmic appearance figure (SEM), 2000 times of magnifications.
Fig. 2 is embodiment 2 preparation titanium anode surface microcosmic appearance figure (SEM), 2000 times of magnifications.
Fig. 3 is embodiment 3 preparation titanium anode RuO
2～IrO
2～TiO
2The cyclic voltammetry curve of/Ti.
Embodiment
The preparation method of modified with noble metals titanium anode material; Adopt the precious metal organic coordination compound as presoma; Presoma is atomized into atomization air flow after being dissolved in organic solvent, is deposited on titanium metal sheet material surface, and has thermolysis down, cooling in rare gas element; Deposition, thermolysis, three successive steps of cooling are repeated more than 1 time, and aftertreatment promptly gets.
In order to obtain and basal body binding force good metal coating, need metal titanium is carried out a series of pre-treatment and surface-treated, comprising: sandblast polishing, alkali cleaning oil removing, ultrasonic acid etching activation.Described ultrasonic acid etching activation is the oxalic acid that the metal titanium base material is placed 10～20% concentration of volume percent, ultrasonic frequency 30～120kHz, ultrasonic power 20～2000W, 60～100 ℃ of ultrasonic activation temperature, 30～80 minutes ultrasonic activation time.Concentration of oxalic acid is excessive to be prone to cause metal titanium substrate excessive corrosion, the too small metal titanium substrate surface activatory purpose that do not reach again of concentration.Activation temperature, soak time are bigger to the influence of metal titanium substrate surface active state, can influence the bonding strength of noble coatings and metal titanium substrate in the subsequent technique, and the catalytic activity of noble coatings.Titanium base material low temperature (0～10 ℃) vacuum-drying after the processing is preserved.
The present invention adopts the precious metal organic coordination compound to replace traditional precious metal chloride and nitrate compound as presoma.The precious metal organic coordination compound is dissolved in the diluting soln that organic solvent is made into 3～8wt% before the atomizing; The concentration of diluting soln causes the coating be full of cracks greatly easily; Influence the anode material life-span; The too small surfactivity layer that then can not effectively protect the metal titanium substrate of concentration has influence on the bonding strength of noble coatings and base metal.
Deposition is carried out in the sediment chamber usually; Carrier gas, atomization air flow and titanium substrate are room temperature; Can be through external heating unit control sediment chamber temperature; The too high meeting of temperature causes the decomposition variation of presomaization and thing during deposition, and temperature is crossed to hang down and can be made presoma change liquid state into by gaseous state again, influences the subsequent deposition effect.
During thermolysis, owing to adopt the precious metal organic coordination compound as presoma, the inorganic salt of its relative precious metal, decomposition temperature is low, and degradation production does not contain NO
xCompound, degradation production are that the precious metal organic coordination compound combines well with the metal titanium substrate, and the contact ohmic resistance is low.
For binary or polynary modified with noble metals titanium anode material; Adopt two kinds or above precious metal organic coordination compound to be made into mixing solutions by a certain percentage; Binary precious metal organic coordination compound is an example with the ruthenium complex of iridium coating with the meaning represented, by volume 1 (methyl ethyl diketone ruthenium): 0.4～1.2 (methyl ethyl diketone iridium) preparation.
For unit modified with noble metals titanium anode material, owing to only adopt a kind of precious metal organic coordination compound as presoma, its decomposition temperature directly has a narrower temperature section at 250～450 ℃, adopts one-part form to decompose and gets final product.And for two or more precious metal organic coordination compound, because different precious metal organic coordination compound decomposition temperatures is different, the difference according to precious metal organic coordination compound prescription can adopt two sections or multistage thermolysis to binary or polynary precious metal.
Below be described in detail two embodiment of the present invention, but the present invention not only is limited to this:
Embodiment 1 single noble coatings titanium anode
Cutting is of a size of the commercial titanium (trade mark TA2) of 100 * 30 * 1.5 (mm) as the metal titanium base material, after surface sand-blasting is handled, with the NaOH solution of weight percent concentration 5% in 70 ℃ of immersions oil removing in 20 minutes.Select the ultrasonic apparatus ultrasonic activation etching of 50kHz ultrasonic frequency, 100W ultrasonic power then for use, adopt 70 ℃ weight percent concentration 10% oxalic acid solution when ultrasonic, ultrasonic time 30 minutes.Pretreated metal titanium base material is kept dry in 10 ℃ of vacuum drying ovens.
Adopt methyl ethyl diketone iridium as presoma, it is dissolved in DMSO 99.8MIN., and is diluted to 3% weight percent concentration.To dilute back solution and place the efficient ultrasonic atomisation unit; Make solution form the atomizing gaseous state; And be that carrier gas imports the sediment chamber with atomization air flow with the argon gas, ar pressure remains 0.1MPa, makes it be deposited on above-mentioned pretreated metal titanium substrate surface; Sediment chamber's temperature is controlled at 80 ℃, depositing time 16 minutes.Then post-depositional metal titanium base material is placed 256 ℃ Ar atmosphere furnace pyrolysis 30 minutes, take out the titanium anode and naturally cool to room temperature, put into the sediment chamber immediately and repeat above-mentioned deposition, thermolysis, natural cooling process, this process repeats 3 times.Place 400 ℃ of retort furnaces to obtain finished product in 60 minutes on the titanium anode after the surface-treated subsequently.
Made modified titanium anodes material coating thickness is 20 microns, and the cyclic voltammetric performance is illustrated in the potential region of 0.2～1.2V, and this coatingsurface liberation of hydrogen does not take place or analyses the chlorine reaction, promptly is in the electrostatic double layer district.Anode volt-ampere electric weight is 111.6mCcm
-2, the anode volt-ampere electric weight that is far superior to the titanium anode material of iridous chloride preparation is 70.3mCcm
-2Strengthen 900 minutes electrode lives, electrode coating surface microscopic topographic such as Fig. 1.
Cutting is of a size of the commercial titanium (trade mark TA2) of 100 * 30 * 1.5 (mm) as the metal titanium base material, after surface sand-blasting is handled, with the NaOH solution of weight percent concentration 5% in 70 ℃ of immersions oil removing in 20 minutes.Select the ultrasonic apparatus ultrasonic activation etching of 50kHz ultrasonic frequency, 100W ultrasonic power then for use, adopt 60 ℃ weight percent concentration 15% oxalic acid solution when ultrasonic, ultrasonic time 45 minutes.Pretreated metal titanium base material kept dry in the low-temperature vacuum drying case.
Adopt the methyl ethyl diketone ruthenium as presoma, it is dissolved in DMSO 99.8MIN., and is diluted to 4% weight percent concentration.To dilute back solution and place the efficient ultrasonic atomisation unit; Make solution form the atomizing gaseous state; And be that carrier gas imports the sediment chamber with atomization air flow with nitrogen, nitrogen pressure remains 0.1MPa, makes it be deposited on above-mentioned pretreated metal titanium substrate surface; Sediment chamber's temperature is controlled at 75 ℃, depositing time 14 minutes.Then post-depositional metal titanium base material is placed 220 ℃ Ar atmosphere furnace pyrolysis 40 minutes, take out the titanium anode and naturally cool to room temperature, put into the sediment chamber immediately and repeat above-mentioned deposition, thermolysis, natural cooling process, this process repeats 3～5 times.Place 390 ℃ of retort furnaces to obtain finished product in 60 minutes on the titanium anode after the surface-treated subsequently.
Made modified titanium anodes material coating thickness is 25 microns, and the cyclic voltammetric performance is illustrated in the potential region of 0.25～1.18V, and this coatingsurface liberation of hydrogen does not take place or analyses the chlorine reaction, promptly is in the electrostatic double layer district.Anode volt-ampere electric weight is 110.23mCcm
-2, the anode volt-ampere electric weight that is superior to the titanium anode material of ruthenium trichloride preparation is 80.17mCcm
-2Strengthening electrode life is 1020 minutes, electrode coating surface microscopic topographic such as Fig. 2.
Embodiment 3 binary noble coatings titanium anodes
Cutting is of a size of the commercial titanium (trade mark TA2) of 100 * 30 * 1.5 (mm) as the metal titanium base material, after surface sand-blasting is handled, with the NaOH solution of weight percent concentration 5% in 70 ℃ of immersions oil removing in 20 minutes.Select the ultrasonic apparatus ultrasonic activation etching of 50kHz ultrasonic frequency, 100W ultrasonic power then for use, adopt 100 ℃ weight percent concentration 20% oxalic acid solution when ultrasonic, ultrasonic activation etching 18 minutes.Kept dry in the low-temperature vacuum drying case subsequently.Adopt methyl ethyl diketone iridium and methyl ethyl diketone ruthenium as presoma, it is dissolved in the organic solvent DMSO 99.8MIN., and is diluted to methyl ethyl diketone iridium 3wt%, the methyl ethyl diketone ruthenium is 5wt%.With 3% methyl ethyl diketone iridium dimethyl sulphoxide solution, with 5% methyl ethyl diketone ruthenium dimethyl sulphoxide solution, mixing in 1: 2 is by volume stirred; Mixing solutions is placed the efficient ultrasonic atomisation unit, make solution form the atomizing gaseous state, and be that carrier gas imports the sediment chamber with atomization air flow with the argon gas; The deposition room temp is controlled at 65 ℃, makes it be deposited on the metal titanium substrate surface, places 290 ℃ of Ar atmosphere furnace pyrolysis 35 minutes with being about to the metal titanium base material; Be incubated after 10 minutes, be warming up to 370 ℃ of reactions 30 minutes again, take out titanium anode naturally cooling; Put into the sediment chamber immediately and deposit next time, this process repeats 3～5 times.Place 400 ℃ of retort furnaces to carry out aftertreatment on the titanium anode after the surface-treated subsequently and obtained finished product in 60 minutes.
Made modified titanium anodes material coating thickness is 32 microns, and titanium anode material surface composition is seen table 1.Cyclic voltammetry curve is seen Fig. 3, and anode volt-ampere electric weight is 140.52mCcm
-2, strengthening electrode life is 1219 minutes.
Table 1RuO
2～IrO
2～TiO
2/ Ti anode surface composition
| Element | Ti | Ru | Ir |
| Per-cent (mol%) | 77.65 | 16.36 | 5.99 |
The titanium anode yield rate that the inventive method makes is high, and surperficial dew point is few, explains that the bonding force of precious metal and pure titanium base material is high, and the homogeneity and the consistence of whole coating are better.And experiment shows the titanium anode electrochemical excellent property that the inventive method makes, long service life.
Claims (10)
1. the preparation method of modified with noble metals titanium anode material; Adopt the precious metal organic coordination compound as presoma; Presoma is atomized into atomization air flow after being dissolved in organic solvent, is deposited on titanium metal sheet material surface, and has thermolysis down, cooling in rare gas element; Deposition, thermolysis, three successive steps of cooling are repeated more than 1 time, and aftertreatment promptly gets.
2. the preparation method of modified with noble metals titanium anode material according to claim 1 is characterized in that: the precious metal organic coordination compound is the title complex that precious metal and organic cpds chelating form; Said organic cpds is for having the organic cpds of
structure, and R1, R2 independently are the C1-C8 alkyl.
3. the preparation method of modified with noble metals titanium anode material according to claim 1 and 2 is characterized in that: said precious metal organic coordination compound is at least a in methyl ethyl diketone platinum, methyl ethyl diketone ruthenium, methyl ethyl diketone rhodium, methyl ethyl diketone iridium, the palladium acetylacetonate.
4. the preparation method of modified with noble metals titanium anode material according to claim 3; It is characterized in that: when said precious metal organic coordination compound was methyl ethyl diketone platinum, methyl ethyl diketone ruthenium, methyl ethyl diketone rhodium, methyl ethyl diketone iridium or palladium acetylacetonate, post-depositional metal titanium base material placed 250～400 ℃ of inert atmosphere stove pyrolysis 20～100 minutes.
5. the preparation method of modified with noble metals titanium anode material according to claim 3; It is characterized in that: when said precious metal organic coordination compound is any two kinds in methyl ethyl diketone platinum, methyl ethyl diketone ruthenium, methyl ethyl diketone rhodium, methyl ethyl diketone iridium, the palladium acetylacetonate; Post-depositional metal titanium base material places inert atmosphere stove pyrolysis; Pyrolysis divides two sections to carry out, 250～350 ℃ of reactions of low-temperature zone 20～45 minutes, 350～400 ℃ of reactions 20～50 minutes.
6. according to the preparation method of each described modified with noble metals titanium anode material of claim 1～5, it is characterized in that: temperature is controlled at 65～80 ℃ during said deposition.
7. the preparation method of modified with noble metals titanium anode material according to claim 6 is characterized in that: said depositing time is 14～20min.
8. according to the preparation method of each described modified with noble metals titanium anode material of claim 1～5, it is characterized in that: said organic solvent is at least a in absolute ethyl alcohol, toluene, the DMSO 99.8MIN..
9. according to the preparation method of each described modified with noble metals titanium anode material of claim 1～5, it is characterized in that: atomization air flow when deposition is carrier gas with the rare gas element, and carrier gas air pressure remains on 0.1～0.2MPa.
10. according to the preparation method of each described modified with noble metals titanium anode material of claim 1～9; It is characterized in that: need pre-treatment before said titanium metal substrates is used; Pre-treatment comprises sandblast polishing, alkali cleaning oil removing or ultrasonic acid etching activation, and the titanium after the processing belongs to the base material low-temperature vacuum drying and preserves.
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| CN109023312A (en) * | 2018-09-05 | 2018-12-18 | 燕山大学 | A kind of method of laser assisted prepares coating Ti electrode |
| CN109950565A (en) * | 2019-03-28 | 2019-06-28 | 中国科学技术大学 | A kind of two-dimentional nano sheets of platinum, preparation method and the application of carbon doping |
| CN110438527A (en) * | 2019-08-05 | 2019-11-12 | 上海氯碱化工股份有限公司 | The preparation method of the transient metal doped anode containing ruthenium coating |
| CN112011799A (en) * | 2020-08-18 | 2020-12-01 | 九江德福科技股份有限公司 | Additive for cleaning titanium anode plate of electrolytic cell and cleaning method |
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| CN110438527A (en) * | 2019-08-05 | 2019-11-12 | 上海氯碱化工股份有限公司 | The preparation method of the transient metal doped anode containing ruthenium coating |
| CN112011799A (en) * | 2020-08-18 | 2020-12-01 | 九江德福科技股份有限公司 | Additive for cleaning titanium anode plate of electrolytic cell and cleaning method |
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