CN104294311A - Making method of platinum iridium oxide alloy electrode - Google Patents
Making method of platinum iridium oxide alloy electrode Download PDFInfo
- Publication number
- CN104294311A CN104294311A CN201410452379.XA CN201410452379A CN104294311A CN 104294311 A CN104294311 A CN 104294311A CN 201410452379 A CN201410452379 A CN 201410452379A CN 104294311 A CN104294311 A CN 104294311A
- Authority
- CN
- China
- Prior art keywords
- platinoiridita
- oxide alloy
- solution
- platinum
- alloy electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a making method of a platinum iridium oxide alloy electrode. The method includes the following steps: heating and stirring a platinum salt and sodium nitrate mixed solution to 55-65DEG C, carrying out evaporating crystallization, drying, grinding, calcining to obtain a mixture, washing the mixture by water to remove impurities, carrying out full wet grinding, and dispersing the wet ground mixture in a solvent to obtain a platinum dioxide solution; dispersing an iridium salt in the solvent, adding the platinum dioxide solution, adjusting the pH value to 14 by using sodium hydroxide, and dissolving and dispersing to obtain a coating solution; and coating a titanium plate with the coating solution, drying, calcining at 400-700DEG C, and cooling in air to obtain the platinum iridium oxide alloy electrode. The above platinum iridium oxide titanium anode electrocatalysis material prepared in the invention has the characteristics of fine crystsal grains and honeycomb shape; and the anodic chlorine evolution electrocatalytic activity is high, and the service life is long, so the electrode is suitable for preparing electrolyzed oxidizing water, and the use cost is reduced.
Description
Technical field
The invention belongs to electrode materials technical field, be specifically related to a kind of preparation method of platinoiridita oxide alloy Ni―Ti anode.
Background technology
In electrochemical industry, the research and development of its gordian technique electrode materials in a cell, anode material the Nomenclature Composition and Structure of Complexes determines its electrochemical activity and stability.In the preparation of chlorine industry, seawater electrolysis and EO water, three is realized by electrolytic chlorination sodium solution, but concentration of sodium chloride solution has very big difference, be respectively 25wt%, 2-5wt% and 0.05-0.1wt%, so large concentration difference causes the difference of electrocatalytic reaction type and electrolytic efficiency, so antianode material requirements also can be different.The particularly preparation of EO water, because its chloride ion content is little, anode not only exists analyses chlorine reaction, also there is a large amount of oxygen evolution reactions, how to allocate reaction preference between the two, improve the electrolytic efficiency analysing chlorine reaction, have vital impact to the germ-killing efficiency of EO water and electrode life.
At present, widely used Ru base precious metal oxide electrode in chlorine industry, it analyses chlorine and oxygen evolution potential only differs 100mV, so when chloride ion content is lower, can produce and a large amount of analyse oxygen electric current, thus destroy the anoxic sosoloid of coating of metal oxides, reduce electrolytic efficiency and work-ing life.Compared with the metal oxide electrode such as Ru base, Ir metal oxides analyse chlorine and oxygen evolution activity a little less than Ru, but to increase considerably the work-ing life of its electrode, but still the actual needs used under being difficult to meet this special conditions.In order to improve its electrolytic efficiency and work-ing life further, some indifferent oxides can be introduced in active coating, chemical stability is provided; As TiO
2, Ta
2o
5, SiO
2, SnO
2deng.In addition, also have part investigator that Pt simple substance is introduced into IrO at present
2middle raising electrode stability, but Pt metal is face-centred cubic structure, and IrO
2rutile-type structure, so cosolvency price differential between the two, and PtO
2and IrO
2the same is all rutile-type structure, and it has higher overpotential for oxygen evolution, if by PtO
2join IrO
2in, good solid solution structure can be formed like this, thus reduce electrode materials oxygen evolution activity, improve and analyse chlorine selectivity, improve electrode life.
At present, little for preparing the research of EO water anode electrode material specially, wherein once new equality people (Tongji University's journal (natural science edition), 2011,39 (9): 1318-1323) reports thermal decomposition method and prepares RuO
2-SnO
2-TiO
2electrode, research shows that it is best that it analyses chlorine activity when Ru content is 25%; But electrode is only 105min accelerated life, can not actual operation requirements be met, in article, also not report that this electrode prepares the performance of EO water.2012, once new equality people (Journal of Electroanalytical Chemistry 677 – 680 (2012) 133 – 138) have studied again Sn content on this basis on the impact preparing EO water electrolytic efficiency and electrode reinforcing life, research shows that electrolytic efficiency is higher when Sn content is less than 10%; When content is 5%, accelerated life is the longest, but is also only 85min, can not meet actual operation requirements equally.2013, great more than University Of Chongqing (University Of Chongqing's Master's thesis, 2013) prepared platinum Ti electrode and ruthenium iridium electrode, found that ruthenium iridium electrode prepares EO water performance and is better than platinum Ti electrode.In addition, the actual service life of platinum Ti electrode reaches 1800h, and the ruthenium iridium electrode of high iridium content reaches 2000h actual service life.Although ruthenium iridium electrode does not reach the requirement (being greater than 3000h) to electrode materials work-ing life in GB GB-28234-2011 yet higher than platinum Ti electrode actual service life.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provides a kind of preparation method of titanium base platinoiridita oxide alloy Ni―Ti anode, obtain the electro catalytic activity of platinoiridita oxide alloy electrode and stability is all significantly improved.
For achieving the above object, adopt technical scheme as follows:
A preparation method for platinoiridita oxide alloy electrode, comprises the following steps:
1) by the mixing solutions of platinum salt and SODIUMNITRATE 55-65 DEG C of heated and stirred, evaporative crystallization, drying, grinding, roasting obtain mixture, ion, and then fully wet grinding, dispersion obtain platinum dioxide solution in a solvent;
2) iridium salt is distributed in solvent, then adds above-mentioned platinum dioxide solution, make concentration of metal ions at 0.05-0.3molL
-1, by sodium hydrate regulator solution pH value to 14, dissolve dispersion, obtain coating solution;
3) the even described coating solution of coating on titanium plate, dries, and then roasting at 400-700 DEG C, cools in atmosphere; Described coating, oven dry, roasting, process of cooling circulation obtain platinoiridita oxide alloy electrode for 5-20 time.
By such scheme, described platinum salt is H
2ptCl
6, K
2ptCl
6, Na
2ptCl
6, (NH
4)
2ptCl
6, PtCl
4, Pt (NH
3)
2(NO
3)
2, PtCl
2(PhCN)
2or PtCl
2(P (C
6h
5)
3)
2.
By such scheme, described iridium salt is Na
2irCl
6, K
2irCl
6, H
2irCl
6, IrCl
3, IrCl
4, IrI
4or Ir (OAC)
3.
By such scheme, step 1) described in the concentration of metal ion in mixing solutions of platinum salt be 0.05-0.3molL
-1, adding sodium nitrate concentration is 0.4-2.4molL
-1.
By such scheme, step 1) and step 2) described in solvent be the mixing of any one or two kinds of ethanol, propyl carbinol, Virahol, hydrochloric acid soln, salpeter solution.
By such scheme, step 2) described in dissolve dispersion process for supersound process and the stir process of hocketing, each 30min 3-10h consuming time.
By such scheme, step 1) and step 3) maturing temperature be 500 DEG C.
By such scheme, step 2) in platinoiridita mol ratio be 1:1.
Beneficial effect of the present invention is:
The crystal grain of obtained platinoiridita oxide compound Ni―Ti anode electrocatalysis material is tiny, and in cellular feature;
Anode to analyse chlorine electro catalytic activity high, and long service life, be more suitable for the preparation of EO water, use cost reduces.
Accompanying drawing explanation
Fig. 1: the field emission scanning electron microscope figure of different ratios platinoiridita oxide alloy Ni―Ti anode in embodiment 1;
Fig. 2: in embodiment 1 different ratios platinoiridita oxide alloy Ni―Ti anode X-ray diffractogram.
Embodiment
Following specific embodiment explains technical scheme of the present invention further, but not as limiting the scope of the invention.
The preparation process of titanium base platinoiridita oxide alloy electrode of the present invention is as follows:
(1) pre-treatment of Titanium base: sandblasting, oil removing, ultrasonic acid etching, cleaning, oven dry;
(2) preparation of platinum dioxide: by the mixing solutions of platinum salt and SODIUMNITRATE 55-65 DEG C of heated and stirred, evaporative crystallization, drying, grinding, roasting obtain mixture, then carry out abundant wet grinding, obtain platinum dioxide solution in dispersion solvent; The concentration of metal ions of platinum salt is 0.05-0.3molL
-1, adding sodium nitrate concentration is 0.4-2.4molL
-1; Described roasting process is sinter 30min at 500 DEG C.
(3) configuration of coating solution: be distributed in solvent by iridium salt, then adds above-mentioned platinum dioxide solution, makes concentration of metal ions at 0.05-0.3molL
-1, then use sodium hydrate regulator solution pH value to 14, dissolve dispersion, obtain coating solution.
(4) the even described coating solution of coating on titanium plate, dries, and then roasting at 400-700 DEG C, cools in atmosphere; Described coating, oven dry, roasting, process of cooling circulation obtain platinoiridita oxide alloy electrode for 5-20 time.
Wherein, platinum salt is chosen as H
2ptCl
6, K
2ptCl
6, Na
2ptCl
6, (NH
4)
2ptCl
6, PtCl
4, Pt (NH
3)
2(NO
3)
2, PtCl
2(PhCN)
2or PtCl
2(P (C
6h
5)
3)
2.
Iridium salt is chosen as Na
2irCl
6, K
2irCl
6, H
2irCl
6, IrCl
3, IrCl
4, IrI
4or Ir (OAC)
3.
Optimally, dissolving dispersion process in above-mentioned steps (3) is supersound process and the stir process of hocketing, each 30min 3-10h consuming time.
Optimally, step 4) in roasting process preferably roasting 10min at 500 DEG C.
Optimally, step 3) in preferably platinoiridita mol ratio be 1:1.
Embodiment 1
By the TA1 titanium plate of 10cm × 5cm first through sandblasting, then be 10% sodium carbonate solution alkali cleaning 10min oil removing with massfraction under ul-trasonic irradiation, then wash with deionized water under ul-trasonic irradiation, at 96 DEG C, 40min is activated again with 10wt% oxalic acid, finally with deionized water rinsing, dry, be kept in dehydrated alcohol.
By 2.590g H
2ptCl
6in the ethanol being dissolved in 50mL volume ratio 1:1 and isopropanol solvent, metal ion in solution concentration is made to be 0.1molL
-1, stir.Then in solution, add SODIUMNITRATE solid 3.400g, stir and be heated to 60 DEG C, Keep agitation is until solvent evaporates is complete.Then mixture is completely dry in the baking oven of 80 DEG C, obtain dry salt mixture, and fully grind in agate mortar, make it mix.Roasting 30min, temperature rise rate 5 DEG C of min at 500 DEG C in tube furnace subsequently
-1, obtain the mixture of salt.After mixture is cooled to room temperature, by its with excessive deionized water wash repeatedly, removing excess salt.Then adding 5ml volume ratio is 1:1 dehydrated alcohol and isopropyl alcohol mixture, after abundant wet grinding, carries out ultrasonic disperse 30min, obtains platinum dioxide solution.
By 0.515g H
2irCl
6being distributed to 5mL volume ratio is that in the ethanol of 1:1 and the mixed solvent of Virahol, dispersed with stirring is even.Then, add platinum dioxide solution 0.00mL, 0.25mL, 1.00mL, 4.00mL obtained above respectively, obtain the platinoiridita oxide alloy of different mol ratio.In addition, adding 5.00mL, 7.25mL, 14.00mL, 41.00mL volume ratio is respectively the ethanol of 1:1 and the mixed solvent of Virahol, makes metal ion in solution concentration be 0.1molL
-1.Then ultrasonic disperse 30min, adds several 2molL
-1solution ph is adjusted to 14 by NaOH, carries out ultrasonic alternate agitation 3h, makes it fully dissolve dispersion, obtain coating solution thus.
Prepared coating solution is put in handtailor container, utilizes uniform fold coating solution on dip-coating method titanium plate after the pre-treatment, pull rate 2cmmin
-1; Then put into loft drier, dry 10min for 80 DEG C, until surface-coated solution is dried; Then put it in retort furnace, roasting 10min at 500 DEG C, make its surface production oxide coating; Then take out from retort furnace, cool in atmosphere.Coating like this, oven dry, sintering, process of cooling circulate 20 times.For the last time, annealing time is 1h, obtains the platinoiridita oxide alloy Ni―Ti anode of different mol ratio.
Electro-chemical test is carried out to the platinoiridita oxide alloy Ni―Ti anode of embodiment 1 gained different mol ratio.Method is as follows, CHI700D electrochemical workstation carries out, and electrolyzer adopts three-electrode system, and supporting electrode is carbon paper electrode, reference electrode is reversible hydrogen reference electrode or saturated calomel electrode, and working electrode is that (apparent area is 1cm for the platinoiridita oxide alloy Ni―Ti anode of different mol ratio
2).At 25 DEG C, 0.5molL
-1h
2sO
4measure in solution and analyse oxygen polarization curve, at saturated NaCl solution (6molL
-1) in measure electrode analyse chlorine polarization curve.As shown in table 1.
Table 1
As can be seen from Table 1, when after formation platinoiridita oxide alloy electrode, it is analysed chlorine activity and significantly improves, and its current density when 1.6V is 1.52,2.18 and 1.86 times of iridium dioxide electrode respectively, wherein analyses chlorine activity during iridium platinum mol ratio 1:1 the highest; And analyse chlorine current density along with the increase of Pt content and constantly reduce, illustrate that its oxygen evolution activity reduces gradually, this is conducive to the work-ing life of improving electrode.
In self-control ion-exchange membrane electrolyzer, anode adopts platinoiridita oxide alloy Ni―Ti anode (the useful area 1cm of embodiment 1 gained different mol ratio
2), negative electrode is Titanium board.Electrolyzer be divide into positive column and cathodic area by centre cationic exchange membrane, and volume is respectively 100mL.In electrolytic process.Interpolation concentration is 1gL
-1naCl solution as ionogen, current density is 100mAcm
-2, interelectrode distance is 4cm, and electrolysis 30min, obtains EO water in positive column, and carries out available chlorine content, pH and oxidizing potential mensuration.As shown in table 2.
Table 2
As can be seen from Table 2, after forming platinoiridita oxide alloy, its electrolysis obtains available chlorine content in EO water and is obviously higher than iridium dioxide electrode, and this comes from the raising that they analyse chlorine reactive behavior, this is consistent with table 1 result, and wherein when platinoiridita mol ratio is 1:1, available chlorine content is maximum.In addition, the change of platinoiridita composition obtains the pH value of EO water to electrolysis and oxidation potential value impact is little.
The field emission scanning electron microscope figure of embodiment 1 gained different ratios platinoiridita oxide alloy Ni―Ti anode, shown in accompanying drawing 1.Fig. 1 (a) is IrO
2sEM figure, it shows the feature of typical oxidation thing coating, in obvious polygon, and can observe tiny crystal grain.The SEM figure of Fig. 1 (b), Fig. 1 (c) and Fig. 1 (d) to be platinoiridita mol ratio be respectively 1:4,1:1 and 4:1.With IrO
2sEM figure different, platinoiridita oxide alloy, in significantly cellular, does not observe obvious crackle, and this is conducive to the work-ing life of improving electrode.When iridium content is more, can observe obvious, a large amount of, tiny crystal grain, this is conducive to improving its electro catalytic activity area.
Embodiment 1 gained different ratios platinoiridita oxide alloy Ni―Ti anode X-ray diffractogram, shown in accompanying drawing 2.As can be seen from the figure IrO
2be typical Rutile Type crystalline structure, contrast JCPDS 15-0870 standard card, it is IrO in the diffraction peak of 27.8 °, 34.7 °, 53.9 ° and 66.6 ° respectively
2the characteristic peak of the crystal face such as (110), (101), (211), (112).And work as IrO
2in mix PtO
2after, after forming sosoloid, it is obvious (101) crystallographic plane diffraction peak at 34.1 ° of places, and this is rutile-type crystal characteristic feature.In addition, (002), (211) and (112) crystal face characteristic peak can also be observed.More than characterize explanation, due to IrO
2and PtO
2both are all rutile-type crystal, there is identical symmetry and close lattice parameter, so can form mixed crystal in extensive ratio range.
Embodiment 2
By the TA1 titanium plate of 10cm × 5cm first through sandblasting, then be 10% sodium carbonate solution alkali cleaning 10min oil removing with massfraction under ul-trasonic irradiation, then wash with deionized water under ul-trasonic irradiation, at 96 DEG C, 40min is activated again with 10wt% oxalic acid, finally with deionized water rinsing, dry, be kept in dehydrated alcohol.
By 2.590g H
2ptCl
6in the ethanol being dissolved in 50mL volume ratio 1:1 and isopropanol solvent, metal ion in solution concentration is made to be 0.1molL
-1, stir.Then in solution, add SODIUMNITRATE solid 3.400g, stir and be heated to 60 DEG C, Keep agitation is until solvent evaporates is complete.Then mixture is completely dry in the baking oven of 80 DEG C, obtain dry salt mixture, and fully grind in agate mortar, make it mix.Roasting 30min, temperature rise rate 5 DEG C of min at 500 DEG C in tube furnace subsequently
-1, obtain the mixture of salt.After mixture is cooled to room temperature, by its with excessive deionized water wash repeatedly, removing excess salt.Then adding 5ml volume ratio is 1:1 dehydrated alcohol and isopropyl alcohol mixture, after abundant wet grinding, carries out ultrasonic disperse 30min, obtains platinum dioxide solution.
By 0.515g H
2irCl
6being distributed to 5mL volume ratio is that in the ethanol of 1:1 and the mixed solvent of Virahol, dispersed with stirring is even.Then, add platinum dioxide solution 1.00mL obtained above, obtain the platinoiridita oxide alloy of mol ratio 1:1.In addition, then to add 14.00mL volume ratio be the ethanol of 1:1 and the mixed solvent of Virahol, makes metal ion in solution concentration be 0.1molL
-1.Then ultrasonic disperse 30min, adds several 2molL
-1solution ph is adjusted to 14 by NaOH, carries out ultrasonic alternate agitation 3h, makes it fully dissolve dispersion, obtain coating solution thus.
Prepared coating solution is put in handtailor container, utilizes uniform fold coating solution on dip-coating method titanium plate after the pre-treatment, pull rate 2cmmin
-1; Then put into loft drier, dry 10min for 80 DEG C, until surface-coated solution is dried; Then put it in retort furnace, respectively roasting 10min at 400-700 DEG C, make its surface production oxide coating; Then take out from retort furnace, cool in atmosphere.Coating like this, oven dry, sintering, process of cooling circulate 20 times.For the last time, annealing time is 1h, obtains the platinoiridita oxide alloy Ni―Ti anode at different heat treatment temperature.
The platinoiridita oxide alloy Ni―Ti anode of different maturing temperature is carried out electro-chemical test.Method is as follows, CHI700D electrochemical workstation carries out, and electrolyzer adopts three-electrode system, and supporting electrode is carbon paper electrode, reference electrode is reversible hydrogen reference electrode or saturated calomel electrode, and working electrode is that (apparent area is 1cm for the platinoiridita oxide alloy Ni―Ti anode of different mol ratio
2).At 25 DEG C, 0.5molL
-1h
2sO
4measure in solution and analyse oxygen polarization curve, at saturated NaCl solution (6molL
-1) in measure electrode analyse chlorine polarization curve.As shown in table 3.As can be seen from Table 3, heat treatments at different obtain platinoiridita oxide alloy electrode to analyse chlorine different with analysing oxygen electro catalytic activity, its trend along with the raising of thermal treatment temp in first increases and then decreases.This is due to when thermal treatment temp is lower, and along with thermal treatment temp improves, electrode surface crystal formation is more complete, so electro catalytic activity improves; But when improving thermal treatment temp further, reunion sintering phenomenon appears in electrode surface, greatly reduces the electro catalytic activity area of electrode surface, decline so it is analysed chlorine and analyses oxygen current density.
Table 3
In self-control ion-exchange membrane electrolyzer, anode adopts platinoiridita oxide alloy Ni―Ti anode (the useful area 1cm of different maturing temperature
2), negative electrode is Titanium board.Electrolyzer be divide into positive column and cathodic area by centre cationic exchange membrane, and volume is respectively 100mL.In electrolytic process.Interpolation concentration is 1gL
-1naCl solution as ionogen, current density is 100mAcm
-2, interelectrode distance is 4cm, and electrolysis 30min, obtains EO water in positive column, and carries out available chlorine content, pH and oxidizing potential mensuration.As shown in table 4.
Table 4
As can be seen from Table 4, with the platinoiridita oxide alloy electrode obtained at different heat treatment temperature for anode prepares EO water, its pH value and oxidation potential value are all relatively, but available chlorine content differs greatly, roasting is that 500 DEG C of its available chlorine contents are maximum, this analyses chlorine and analyses oxygen curent change rule consistent with table 3, illustrates that its best preparation temperature is 500 DEG C.
Embodiment 3
By the TA1 titanium plate of 10cm × 5cm first through sandblasting, then be 10% sodium carbonate solution alkali cleaning 10min oil removing with massfraction under ul-trasonic irradiation, then wash with deionized water under ul-trasonic irradiation, at 96 DEG C, 40min is activated again with 10wt% oxalic acid, finally with deionized water rinsing, dry, be kept in dehydrated alcohol.
By 2.590g H
2ptCl
6in the ethanol being dissolved in 25mL volume ratio 1:1 and n-butanol solvent, metal ion in solution concentration is made to be 0.2molL
-1, stir.Then in solution, add SODIUMNITRATE solid 3.400g, stir and be heated to 60 DEG C, Keep agitation is until solvent evaporates is complete.Then mixture is completely dry in the baking oven of 80 DEG C, obtain dry salt mixture, and fully grind in agate mortar, make it mix.Roasting 30min, temperature rise rate 5 DEG C of min at 500 DEG C in tube furnace subsequently
-1, obtain the mixture of salt.After mixture is cooled to room temperature, by its with excessive deionized water wash repeatedly, removing excess salt.Then adding 5ml volume ratio is 1:1 dehydrated alcohol and isopropyl alcohol mixture, after abundant wet grinding, carries out ultrasonic disperse 30min, obtains platinum dioxide solution.
By 0.515g H
2irCl
6being distributed to 5mL volume ratio is that in the ethanol of 1:1 and the mixed solvent of propyl carbinol, dispersed with stirring is even.Then, add platinum dioxide solution 1.00mL obtained above, obtain the platinoiridita oxide alloy of mol ratio 1:1.In addition, then to add 4.00mL volume ratio be the ethanol of 1:1 and the mixed solvent of Virahol, makes metal ion in solution concentration be 0.2molL
-1.Then ultrasonic disperse 30min, adds several 2molL
-1solution ph is adjusted to 14 by NaOH, carries out ultrasonic alternate agitation 6h, makes it fully dissolve dispersion, obtain coating solution thus.
Prepared coating solution is put in handtailor container, utilizes uniform fold coating solution on dip-coating method titanium plate after the pre-treatment, pull rate 4cmmin
-1; Then put into loft drier, dry 10min for 80 DEG C, until surface-coated solution is dried; Then put it in retort furnace, roasting 10min at 500 DEG C, make its surface production oxide coating; Then take out from retort furnace, cool in atmosphere.Coating like this, oven dry, sintering, process of cooling circulate 20 times.For the last time, annealing time is 1h, obtains platinoiridita oxide alloy Ni―Ti anode.In self-control ion-exchange membrane electrolyzer, using this electrode as anode material (useful area 1cm
2), negative electrode is Titanium board.Electrolyzer be divide into positive column and cathodic area by centre cationic exchange membrane, and volume is respectively 100mL.In electrolytic process.Interpolation concentration is 1gL
-1naCl solution as ionogen, current density is 100mAcm
-2, interelectrode distance is 4cm, and electrolysis 30min, obtains EO water in positive column, and its available chlorine content is 162.46mg.L
-1, pH value be 2.21 and oxidizing potential be 1170mV.
Embodiment 4
By the TA1 titanium plate of 10cm × 5cm first through sandblasting, then be 10% sodium carbonate solution alkali cleaning 10min oil removing with massfraction under ul-trasonic irradiation, then wash with deionized water under ul-trasonic irradiation, at 96 DEG C, 40min is activated again with 10wt% oxalic acid, finally with deionized water rinsing, dry, be kept in dehydrated alcohol.
By 2.430g K
2ptCl
6in the ethanol being dissolved in 25mL volume ratio 1:1 and hydrochloric acid solvent, metal ion in solution concentration is made to be 0.2molL
-1, stir.Then in solution, add SODIUMNITRATE solid 3.400g, stir and be heated to 60 DEG C, Keep agitation is until solvent evaporates is complete.Then mixture is completely dry in the baking oven of 80 DEG C, obtain dry salt mixture, and fully grind in agate mortar, make it mix.Roasting 30min, temperature rise rate 5 DEG C of min-at 500 DEG C in tube furnace subsequently
1, obtain the mixture of salt.After mixture is cooled to room temperature, by its with excessive deionized water wash repeatedly, removing excess salt.Then adding 5ml volume ratio is 1:1 dehydrated alcohol and isopropyl alcohol mixture, after abundant wet grinding, carries out ultrasonic disperse 30min, obtains platinum dioxide solution.
By 0.559g Na
2irCl
6being distributed to 5mL volume ratio is that in the ethanol of 1:1 and the mixed solvent of Virahol, dispersed with stirring is even.Then, add platinum dioxide nano-solution 1.00mL obtained above, obtain the platinoiridita oxide alloy of mol ratio 1:1.In addition, then to add 4.00mL volume ratio be the ethanol of 1:1 and the mixed solvent of Virahol, makes metal ion in solution concentration be 0.2molL
-1.Then ultrasonic disperse 30min, adds several 2molL
-1solution ph is adjusted to 14 by NaOH, carries out ultrasonic alternate agitation 6h, makes it fully dissolve dispersion, obtain coating solution thus.
Prepared coating solution is put in handtailor container, utilizes uniform fold coating solution on dip-coating method titanium plate after the pre-treatment, pull rate 8cmmin
-1; Then put into loft drier, dry 20min for 80 DEG C, until surface-coated solution is dried; Then put it in retort furnace, roasting 20min at 500 DEG C, make its surface production oxide coating; Then take out from retort furnace, cool in atmosphere.Coating like this, oven dry, sintering, process of cooling circulate 20 times.For the last time, annealing time is 1h, obtains platinoiridita oxide alloy Ni―Ti anode.In self-control ion-exchange membrane electrolyzer, using this electrode as anode material (useful area 1cm
2), negative electrode is Titanium board.Electrolyzer be divide into positive column and cathodic area by centre cationic exchange membrane, and volume is respectively 100mL.In electrolytic process.Interpolation concentration is 1gL
-1naCl solution as ionogen, current density is 100mAcm
-2, interelectrode distance is 4cm, and electrolysis 30min, obtains EO water in positive column, and its available chlorine content is 169.04mg.L
-1, pH value be 2.25 and oxidizing potential be 1163mV
Embodiment 5
By the TA1 titanium plate of 10cm × 5cm first through sandblasting, then be 10% sodium carbonate solution alkali cleaning 10min oil removing with massfraction under ul-trasonic irradiation, then wash with deionized water under ul-trasonic irradiation, at 96 DEG C, 40min is activated again with 10wt% oxalic acid, finally with deionized water rinsing, dry, be kept in dehydrated alcohol.
By 2.590g H
2ptCl
6in the ethanol being dissolved in 25mL volume ratio 1:1 and isopropanol solvent, metal ion in solution concentration is made to be 0.2molL
-1, stir.Then in solution, add SODIUMNITRATE solid 3.400g, stir and be heated to 60 DEG C, Keep agitation is until solvent evaporates is complete.Then mixture is completely dry in the baking oven of 80 DEG C, obtain dry salt mixture, and fully grind in agate mortar, make it mix.Roasting 30min, temperature rise rate 5 DEG C of min at 500 DEG C in tube furnace subsequently
-1, obtain the mixture of salt.After mixture is cooled to room temperature, by its with excessive deionized water wash repeatedly, removing excess salt.Then adding 5ml volume ratio is 1:1 dehydrated alcohol and isopropyl alcohol mixture, after abundant wet grinding, carries out ultrasonic disperse 30min, obtains platinum dioxide solution.
By 0.299g IrCl
3being distributed to 5mL volume ratio is that in the ethanol of 1:1 and the mixed solvent of Virahol, dispersed with stirring is even.Then, add platinum dioxide solution 1.00mL obtained above, obtain the platinoiridita oxide alloy of mol ratio 1:1.In addition, then to add 4.00mL volume ratio be the ethanol of 1:1 and the mixed solvent of Virahol, makes metal ion in solution concentration be 0.2molL
-1.Then ultrasonic disperse 30min, adds several 2molL
-1solution ph is adjusted to 14 by NaOH, carries out ultrasonic alternate agitation 6h, makes it fully dissolve dispersion, obtain coating solution thus.
Prepared coating solution is put in handtailor container, utilizes uniform fold coating solution on dip-coating method titanium plate after the pre-treatment, pull rate 5cmmin
-1; Then put into loft drier, dry 30min for 80 DEG C, until surface-coated solution is dried; Then put it in retort furnace, roasting 20min at 500 DEG C, make its surface production oxide coating; Then take out from retort furnace, cool in atmosphere.Coating like this, oven dry, sintering, process of cooling circulate 20 times.For the last time, annealing time is 1h, obtains platinoiridita oxide alloy Ni―Ti anode, and carries out reinforcing life test and electrolytic efficiency mensuration.
Strengthening experimental lifetime test: adopt 2cm × 2cm Ti plate as negative electrode, respectively with 1cm × 1cm embodiment 5 gained Ir
0.5pt
0.5o
2in/Ti, embodiment 1, the pure iridium dioxide of gained is anode, and electrolytic solution is 0.5molL
-1h
2sO
4, temperature 40 DEG C, current density 2Acm
-2.
Electrolytic efficiency measures: in initial soln, chloride ion content is 607mgL
-1, liquor capacity 120mL, current density 100mAcm
-2, electrode area 1cm
2, electrolysis time 0.5h.Anode adopts embodiment 5 gained Ir respectively
0.5pt
0.5o
2the pure iridium dioxide of gained in/Ti, embodiment 1.After electrolysis, chlorine ion content determination adopts potentiometric titration, and working electrode is Ag electrode, the two salt bridge saturated calomel electrode of reference electrode.And calculate electrolytic efficiency by residual nitrogen ion content in solution.The results are shown in Table shown in 5.
Table 5
As can be seen from Table 5, the reinforcing life of platinoiridita oxide alloy is 350h, is 3.5 times of iridium dioxide electrode, illustrates that platinoiridita oxide alloy electrode improves the work-ing life of electrode effectively, makes it have more practicality.Because EO water is when prepared by reality, current density is only 0.1 ~ 0.2Acm
-2, so be 8791h according to formula to calculating its actual service life, meet the requirement of GB GB-28234-2011.In addition, electrolytic preparation EO water is carried out to sodium-chlor dilute solution, and after measuring electrolysis chloride ion content and calculate electrolytic efficiency, as shown in table 5, wherein with platinoiridita oxide alloy for residual chlorine ion content during anode is less than iridium dioxide electrode, so its electrolytic efficiency is higher, be more suitable for as EO water electrolytic anode material.
Claims (8)
1. a preparation method for platinoiridita oxide alloy electrode, is characterized in that comprising the following steps:
1) by the mixing solutions of platinum salt and SODIUMNITRATE 55-65 DEG C of heated and stirred, evaporative crystallization, drying, grinding, roasting obtain mixture, ion, and then fully wet grinding, dispersion obtain platinum dioxide solution in a solvent;
2) iridium salt is distributed in solvent, then adds above-mentioned platinum dioxide solution, make concentration of metal ions at 0.05-0.3molL
-1, by sodium hydrate regulator solution pH value to 14, dissolve dispersion, obtain coating solution;
3) the even described coating solution of coating on titanium plate, dries, and then roasting at 400-700 DEG C, cools in atmosphere; Described coating, oven dry, roasting, process of cooling circulation obtain platinoiridita oxide alloy electrode for 5-20 time.
2. the preparation method of platinoiridita oxide alloy electrode as claimed in claim 1, is characterized in that described platinum salt is H
2ptCl
6, K
2ptCl
6, Na
2ptCl
6, (NH
4)
2ptCl
6, PtCl
4, Pt (NH
3)
2(NO
3)
2, PtCl
2(PhCN)
2or PtCl
2(P (C
6h
5)
3)
2.
3. the preparation method of platinoiridita oxide alloy electrode as claimed in claim 1, is characterized in that described iridium salt is Na
2irCl
6, K
2irCl
6, H
2irCl
6, IrCl
3, IrCl
4, IrI
3or Ir (OAC)
3.
4. the preparation method of platinoiridita oxide alloy electrode as claimed in claim 1, is characterized in that step 1) described in the concentration of metal ion in mixing solutions of platinum salt be 0.05-0.3molL
-1, adding sodium nitrate concentration is 0.4-2.4molL
-1.
5. the preparation method of platinoiridita oxide alloy electrode as claimed in claim 1, is characterized in that step 1) and step 2) described in solvent be the mixing of any one or two kinds of ethanol, propyl carbinol, Virahol, hydrochloric acid soln, salpeter solution.
6. the preparation method of platinoiridita oxide alloy electrode as claimed in claim 1, is characterized in that step 2) described in dissolve dispersion process for supersound process and the stir process of hocketing, each 30min 3-10h consuming time.
7. the preparation method of platinoiridita oxide alloy electrode as claimed in claim 1, is characterized in that step 1) and step 3) maturing temperature be 500 DEG C.
8. the preparation method of platinoiridita oxide alloy electrode as claimed in claim 1, is characterized in that step 2) in platinum, iridium mol ratio be 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410452379.XA CN104294311B (en) | 2014-09-05 | 2014-09-05 | Making method of platinum iridium oxide alloy electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410452379.XA CN104294311B (en) | 2014-09-05 | 2014-09-05 | Making method of platinum iridium oxide alloy electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104294311A true CN104294311A (en) | 2015-01-21 |
| CN104294311B CN104294311B (en) | 2017-04-12 |
Family
ID=52314254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410452379.XA Active CN104294311B (en) | 2014-09-05 | 2014-09-05 | Making method of platinum iridium oxide alloy electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104294311B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803482A (en) * | 2016-03-17 | 2016-07-27 | 同济大学 | Modification method for collector electrode material of electrolytic cell for water-electrolytic hydrogen making, and application |
| CN108736021A (en) * | 2017-04-19 | 2018-11-02 | 昆明仁旺科技有限公司 | A kind of carbon carries the preparation method of porous hollow platinumiridio nano-particle catalyst |
| CN112522728A (en) * | 2020-12-29 | 2021-03-19 | 上海交通大学 | Trace oxygen generation module and pure oxygen generation system thereof |
| CN113430555A (en) * | 2021-06-28 | 2021-09-24 | 湖南紫潇新材料有限责任公司 | Iridium oxide-platinum composite nano catalyst, preparation method and application thereof |
| CN114645295A (en) * | 2022-03-31 | 2022-06-21 | 华南理工大学 | Preparation method of anode catalyst for water electrolysis |
| CN115872466A (en) * | 2022-12-15 | 2023-03-31 | 苏州擎动动力科技有限公司 | Iridium oxide and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974770A (en) * | 2010-11-18 | 2011-02-16 | 北京航空航天大学 | Aqueous solution for electrodepositing iridium layer and method for preparing iridium layer in aqueous solution by way of electrodeposition |
-
2014
- 2014-09-05 CN CN201410452379.XA patent/CN104294311B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974770A (en) * | 2010-11-18 | 2011-02-16 | 北京航空航天大学 | Aqueous solution for electrodepositing iridium layer and method for preparing iridium layer in aqueous solution by way of electrodeposition |
Non-Patent Citations (3)
| Title |
|---|
| ADAMS R: "Bifunctional oxygen electrode with corrosion-resistive gas diffusion layer for unitized regenerative fuel cell", 《J. AM. CHEM. SOC》 * |
| SONG S D: "Bifunctional oxygen electrode with corrosion-resistive gas diffusion layer for unitized regenerative fuel cell", 《ELECTROCHEM. COMMUN》 * |
| 胡杰珍: "含铱钛氧化物中间层的氧化物阳极制备及应用", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803482A (en) * | 2016-03-17 | 2016-07-27 | 同济大学 | Modification method for collector electrode material of electrolytic cell for water-electrolytic hydrogen making, and application |
| CN108736021A (en) * | 2017-04-19 | 2018-11-02 | 昆明仁旺科技有限公司 | A kind of carbon carries the preparation method of porous hollow platinumiridio nano-particle catalyst |
| CN108736021B (en) * | 2017-04-19 | 2021-04-06 | 昆明仁旺科技有限公司 | Preparation method of carbon-supported porous hollow platinum-iridium alloy nanoparticle catalyst |
| CN112522728A (en) * | 2020-12-29 | 2021-03-19 | 上海交通大学 | Trace oxygen generation module and pure oxygen generation system thereof |
| CN113430555A (en) * | 2021-06-28 | 2021-09-24 | 湖南紫潇新材料有限责任公司 | Iridium oxide-platinum composite nano catalyst, preparation method and application thereof |
| CN113430555B (en) * | 2021-06-28 | 2022-09-09 | 湖南紫潇新材料有限责任公司 | Iridium oxide-platinum composite nano catalyst, preparation method and application thereof |
| CN114645295A (en) * | 2022-03-31 | 2022-06-21 | 华南理工大学 | Preparation method of anode catalyst for water electrolysis |
| CN114645295B (en) * | 2022-03-31 | 2023-06-02 | 华南理工大学 | Preparation method of anode catalyst for water electrolysis |
| CN115872466A (en) * | 2022-12-15 | 2023-03-31 | 苏州擎动动力科技有限公司 | Iridium oxide and preparation method thereof |
| CN115872466B (en) * | 2022-12-15 | 2023-09-08 | 苏州擎动动力科技有限公司 | Iridium oxide and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104294311B (en) | 2017-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104294311B (en) | Making method of platinum iridium oxide alloy electrode | |
| US9677183B2 (en) | Electrocatalyst, electrode coating and electrode for the preparation of chlorine | |
| CN104087970B (en) | A kind of rich surface cupric oxide doped iridium dioxide Ni-Ti anode containing iridium dioxide and preparation method thereof | |
| de OS Santos et al. | New laser-based method for the synthesis of stable and active Ti/SnO2–Sb anodes | |
| CN102766882B (en) | A kind of preparation method analysing chlorine DSA electro catalytic electrode of three-dimensional structure | |
| US20170067172A1 (en) | Catalyst coating and process for production thereof | |
| Deng et al. | Preparation of electrolyzed oxidizing water by TiO2 doped IrO2-Ta2O5 electrode with high selectivity and stability for chlorine evolution | |
| Hao et al. | Preparation and characterization of titanium-based PbO 2 electrodes modified by ethylene glycol | |
| JP3319887B2 (en) | Method for producing hypochlorite | |
| KR20230038437A (en) | Anode for electrolysis and preparation method thereof | |
| EP2841624B1 (en) | An electrochemical process for water splitting using porous co3o4 nanorods | |
| CN108611659B (en) | High-efficiency stable Co3O4Nanoribbon array chlorine evolution electrode | |
| Jin et al. | Preparation and characterization of Ce and PVP co-doped PbO2 electrode for waste water treatment | |
| CN108649242B (en) | Preparation method of two-dimensional porous Pt nanosheet, material obtained by preparation method and application of material | |
| CN110318068A (en) | Ion-exchange membrane electrolyzer anodic coating | |
| CN115505951A (en) | Porous iridium oxide nano material, preparation method and application thereof | |
| CN115807241A (en) | Ultrathin iridium-based nanosheet catalyst, and preparation method and application thereof | |
| US20110308939A1 (en) | Electrode for electrolytic production of chlorine | |
| CN110129821A (en) | Tin, Sb doped titanium-based ruthenic oxide coated electrode preparation method | |
| CN107051431B (en) | A kind of active masking liquid and preparation method thereof for analysing chloride electrode | |
| CN104233366B (en) | Preparation method of iridium and copper oxide alloy cathode catalyst | |
| CN110230072A (en) | A kind of preparation method and application of the N-NiZnCu LDH/rGO nano-chip arrays material in nickel foam | |
| Spasojevic et al. | Development of RuO 2/TiO 2 titanium anodes and a device for in situ active chlorine generation | |
| CN103924262B (en) | The hydro-thermal method preparation method containing ruthenium coating catalyst | |
| CN114105219A (en) | Method for preparing cobaltosic oxide material through eutectic ionic liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201223 Address after: 2 / F, No.5, daijiashan science and technology venture City, 888 Hanhuang Road, Jiang'an District, Wuhan City, Hubei Province, 430000 Patentee after: WUHAN LIHUI NEW TECHNOLOGY Co.,Ltd. Address before: 430023 No. 68 Xuefu South Road, Changqing Garden, Hankou, Wuhan, Hubei. Patentee before: Wuhan University of Light Industry Patentee before: WUHAN LIHUI NEW TECHNOLOGY Co.,Ltd. |