CN110983366A - Electrocatalytic coating composition, dimensionally stable anode, preparation method and application - Google Patents
Electrocatalytic coating composition, dimensionally stable anode, preparation method and application Download PDFInfo
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- CN110983366A CN110983366A CN201911401481.6A CN201911401481A CN110983366A CN 110983366 A CN110983366 A CN 110983366A CN 201911401481 A CN201911401481 A CN 201911401481A CN 110983366 A CN110983366 A CN 110983366A
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- 239000008199 coating composition Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 103
- 239000002184 metal Substances 0.000 claims abstract description 96
- 150000003839 salts Chemical class 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 117
- 238000000576 coating method Methods 0.000 claims description 59
- 239000011248 coating agent Substances 0.000 claims description 58
- 238000005245 sintering Methods 0.000 claims description 51
- 239000003054 catalyst Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- 229920001223 polyethylene glycol Polymers 0.000 claims description 19
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 9
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 7
- 229910010298 TiOSO4 Inorganic materials 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000008223 sterile water Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 abstract description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052801 chlorine Inorganic materials 0.000 abstract description 31
- 239000001301 oxygen Substances 0.000 abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 77
- 239000010936 titanium Substances 0.000 description 72
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 38
- 229910052719 titanium Inorganic materials 0.000 description 38
- 239000000203 mixture Substances 0.000 description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- 238000002791 soaking Methods 0.000 description 28
- 239000004334 sorbic acid Substances 0.000 description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 24
- 238000001035 drying Methods 0.000 description 22
- 238000005406 washing Methods 0.000 description 17
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 16
- 238000005498 polishing Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005238 degreasing Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 235000006408 oxalic acid Nutrition 0.000 description 8
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 8
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- 229910021549 Vanadium(II) chloride Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000000645 desinfectant Substances 0.000 description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 3
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- 229910052741 iridium Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead(II) nitrate Inorganic materials [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6445—Antimony
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- B01J35/33—
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
An electrocatalytic coating composition, a dimensionally stable anode, a preparation method and application thereof, wherein the electrocatalytic coating composition comprises a precursor solution of a catalytic active component and an additive; wherein: the precursor solution comprises Ru metal salt, Ti metal salt and one of optional Sn metal salt, Pb metal salt and Sb metal salt; the additive comprises polycarboxylic acid and polyhydric alcohol; wherein the ratio of the polycarboxylic acid to the polyol in the additive is 0.5-1 according to the molar ratio of carboxyl to hydroxyl; and the molar ratio of the total moles of the metal elements in the precursor solution of the catalytic active component to the moles of the polycarboxylic acid is 1: 1-3: 1. The chlorine evolution potential of the dimensionally stable anode obtained by the method can be as low as 1.42V vs. SCE, the difference between the chlorine evolution potential and the oxygen evolution potential reaches 0.57V vs. SCE, and the polarizability is as low as 0.072V vs. SCE. The dimensionally stable anode is used for electrolyzing sodium chloride solution with low concentration, and the electrochemical performance of the dimensionally stable anode is obviously improved.
Description
Technical Field
The invention belongs to the field of electrochemical catalysis application, and particularly relates to an electrocatalytic coating composition, a dimensionally stable anode, a preparation method and application.
Background
Hypochlorous acid or hypochlorite disinfectants are the most commonly used and most effective disinfectants in sewage treatment, food industry and environmental protection, and can be prepared by electrochemical catalytic oxidation of salt water. The anode is a generating source of electrochemical catalytic oxidation reaction, and is directly oxidized or indirectly oxidized; selection of anode materialsThe electrochemical water treatment effect has a crucial influence. The influence factors of hypochlorous acid or hypochlorite concentration are related to the electrode spacing, external voltage, NaCl concentration, pH value and other factors, and are more critical to the electrochemical activity of the catalytic coating of the anode, most patents do not relate to the electrode composition and the electrochemical activity, particularly to the Cl of the anode-The key factors of the electrocatalysis catalyst such as composition, structure, texture and the like. The DSC anode (dimensionally stable anode) is prepared by adhering the metal with strong catalytic activity or the oxide coating thereof on the surface of a substrate by using methods such as brushing sintering or chemical deposition and the like, and calcining the obtained product. The wetting condition of the coating composition and system and the metal matrix and the control of the sintering process have important influence on the distribution of active components on the surface of the electrode, pores and adhesion; in the traditional process, alcohol or water solution containing metal salt is directly coated on a metal titanium sheet, and the metal titanium sheet is dried and then calcined at high temperature; because the salt precipitation caused by the volatilization of the used alcohol has poor binding force with the metal matrix, the catalyst coating usually falls off; in addition, the poor compatibility of different metal oxides after sintering is not matched with thermal shrinkage, a large number of cracks are caused, and the stability and the service life of the electrode coating are reduced. Therefore, a chemical modification method is used to improve the compatibility between the sintered metal oxides; common modifiers include metal oxides such as Sn, Mn, Sb, Ir, and the like. Such as: sn element added modified Ti/IrO23RuO2The surface crack distribution of the electrode is changed, and the flatness of the electrode is greatly improved; the precipitation of cluster crystal grains is weakened, and the electrocatalytic activity to C1 & lt- & gt is improved; but still has the problems of noble metal waste, uneven catalyst coating and the like caused by the falling of mixed metal salt due to solvent volatilization in the step of coating the electrocatalyst, and seriously influences the catalytic effect, the current efficiency and the service life of the electrode in the operation process of the electrode.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide an electrocatalytic coating composition, dimensionally stable anode, preparation method and use, which are intended to at least partially solve at least one of the above mentioned technical problems.
As an aspect of the present invention, there is provided an electrocatalytic coating composition comprising a precursor solution of a catalytically active component and an additive; wherein:
the precursor solution of the catalytic active component comprises Ru metal salt, Ti metal salt and one of optional Sn metal salt, Pb metal salt and Sb metal salt;
the additive comprises polycarboxylic acid and polyhydric alcohol;
wherein the ratio of the polycarboxylic acid to the polyol in the additive is 0.5-1 according to the molar ratio of carboxyl to hydroxyl; and the molar ratio of the total moles of the metal elements in the precursor solution of the catalytic active component to the moles of the polycarboxylic acid is 1: 1-3: 1.
As another aspect of the present invention, there is also provided a method of preparing a dimensionally stable anode, comprising the steps of:
uniformly mixing the electrocatalytic coating composition, and carrying out a gelling reaction to obtain a mixed sol;
dipping a metal matrix in the mixed sol, and sintering the metal matrix dipped with the mixed gel to obtain the metal matrix containing the catalyst coating;
and repeating the dipping and sintering processes on the metal substrate containing the catalyst coating to obtain the dimensionally stable anode.
As a further aspect of the invention, there is also provided a dimensionally stable anode, prepared by the above-described preparation method.
As a further aspect of the invention, there is also provided the use of a dimensionally stable anode as described above in the field of the preparation of sterile water by electrolysis of a sodium chloride solution.
Based on the technical scheme, compared with the prior art, the invention has at least one or part of the following beneficial effects:
different from the prior solvent volatilization process, the invention utilizes the sol reaction of citric acid and polyethylene glycol to form hydrophilic viscous mixed sol, increases the adhesive property of the catalytic active component on the metal titanium substrate, and improves the high-temperature sintering property of the electrode catalytic coating;
different from the prior technical scheme, the invention utilizes the pre-carbonization of low-temperature polymer gel to form carbide, inhibits the excessive growth of electrode mixed oxide particles, prevents the shrinkage caused by thermal stress and inhibits the growth of cracks; improve the surface flatness and quality of the electrode and prolong the service life of the electrode.
The simple preparation process suitable for various inorganic electrocatalyst coatings, provided by the invention, has the advantages of simple and convenient operation process, and is beneficial to improving the utilization rate of catalytic active components and reducing the production cost.
Description of the figures and accompanying tables
FIG. 1 is a scanning electron microscope image of a representative surface topography of a DSC anodic coating prepared in example 3 of the present invention;
FIG. 2 is a representative scanning electron micrograph of the surface of a DSC anodic coating prepared in comparative example 1 of the present invention;
FIG. 3 is a graph showing the change of concentration of active chlorine generated in the anode region of an electrolytic cell assembled by a DSC anode obtained in example 3 of the present invention with respect to electrolysis time.
Detailed Description
The invention provides an electrocatalytic coating composition, a dimensionally stable anode, a preparation method and application, wherein a high molecular polymer sticky sol fixed catalytic active metal mixed salt is formed by utilizing the reaction of organic polybasic acid and polyalcohol, and the adhesion of an electrocatalyst precursor mixed salt on metal titanium is increased; can effectively prevent falling off; in the pre-sintering process, the polymer sol is partially pyrolyzed to fix the mixed metal oxide, so that the sintering performance is improved; the flatness and the electrocatalysis performance of the catalyst coating are improved.
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
As an aspect of the present invention, there is provided an electrocatalytic coating composition comprising a precursor solution of a catalytically active component and an additive; wherein:
the precursor solution of the catalytic active component comprises Ru metal salt, Ti metal salt and one of optional Sn metal salt, Pb metal salt and Sb metal salt;
the additive comprises polycarboxylic acid and polyalcohol;
wherein, the ratio of the polycarboxylic acid to the polyol in the additive is 0.5-1 according to the molar ratio of carboxyl/hydroxyl; and the molar ratio of the total mole of the metal elements in the precursor solution of the catalytic active component to the mole of the polycarboxylic acid is 1: 1-3: 1.
In the embodiment of the invention, a precursor solution comprising Ru metal salt, Ti metal salt and optionally one of Sn metal salt, Pb metal salt and Sb metal salt is used as a catalytic active component, the obtained electrocatalytic coating is applied to a dimensionally stable anode, the electrocatalytic effect of the electrocatalytic coating can realize that the chlorine evolution potential can be as low as 1.42V vs. SCE, the difference between the chlorine evolution potential and the oxygen evolution potential can be as low as 0.57V vs. SCE, and the polarizability can be as low as 0.072V vs. SCE. The dimensionally stable anode is used for electrolyzing sodium chloride solution with low concentration, and the electrochemical performance of the dimensionally stable anode is obviously improved.
It is worth mentioning that the Ti metal salt is soluble, making its operation simpler.
In an embodiment of the invention, the precursor solution of the catalytically active component comprises SnCl4、RuCl3、TiOSO4Mixed of (2) Pb (NO)3)2、RuCl3、TiOSO4Mixed or SbCl of3、RuCl3、TiOSO4And (3) mixing.
In the embodiment of the present invention, TiOSO is selected4The soluble salt has simpler preparation and more common practicability.
In the examples of the present invention, the molar ratio of the metal element in the precursor solution of the catalytically active component is (Sn, Pb or Sb)/Ru/Ti ═ x/(3-x)/7; wherein the value range of x is 0.01-1.5;
preferably, the total molar concentration of the metal elements is 0.2mol/L to 0.4 mol/L.
In embodiments of the invention, the polycarboxylic acid comprises citric acid;
preferably, the concentration of the polycarboxylic acid in the additive is 0.05mol/L to 0.1 mol/L.
In embodiments of the invention, the polyol comprises polyethylene glycol;
preferably, the polyhydric alcohol is polyethylene glycol with the molecular weight of 300-1000.
In the embodiment of the invention, polyethylene glycol with the molecular weight of 300-1000 and polycarboxylic acid are selected to carry out a gelling reaction, so that the surface flatness and the bonding property of the formed coating are improved.
As another aspect of the present invention, there is also provided a method of preparing a dimensionally stable anode, comprising the steps of:
uniformly mixing the electrocatalytic coating composition, and carrying out a gelling reaction to obtain a mixed sol;
dipping a metal matrix in the mixed sol, and sintering the metal matrix dipped with the mixed gel to obtain the metal matrix containing the catalyst coating;
and repeating the dipping and sintering processes on the metal substrate containing the catalyst coating to obtain the dimensionally stable anode.
In an embodiment of the present invention, the conditions of the gelation reaction include: the temperature is 90-120 ℃, more specifically, the heating can adopt oil bath, but is not limited to the oil bath, and other heating modes can also be adopted; stirring speed is 150 rpm-400 rpm, stirring is continued for 1 hour-3 hours, and then the viscous mixed sol is cooled to room temperature to obtain the viscous mixed sol coating.
In the embodiment of the present invention, the dipping and sintering process is repeated 10 to 15 times;
preferably, the specific operating conditions of sintering include: sintering at 250-300 ℃ for 30-50 minutes, and rapidly cooling to room temperature after sintering;
more specifically, the metal matrix is soaked in the mixed sol for 10-20 minutes; then baking the mixture in an oven at the temperature of between 80 and 120 ℃ for 0.5 to 1 hour; and then, quickly transferring the mixture into a muffle furnace to sinter the mixture at the temperature of between 250 and 300 ℃ for 30 to 50 minutes, and quickly cooling the mixture to room temperature after the sintering is finished.
Wherein, the metal matrix adopts a metal titanium sheet, and the surface pre-purification step comprises: polishing a metal titanium sheet by 800-mesh abrasive paper, and then polishing by 2000-mesh abrasive paper; washing with ultrapure water, and soaking in acetone for degreasing; washing with acetone for 2-3 times, and drying; then, the metal titanium sheet is put into oxalic acid solution with the temperature of 90 ℃ to 3 percent to be soaked for 1 to 2 hours, and then is washed clean by water for standby.
Preferably, the temperature of the last sintering is 250-300 ℃, the sintering time is 30-50 minutes, then the temperature is raised to 400-450 ℃ at the speed of 2 ℃/min, the temperature is kept for 1-2 hours, and finally the temperature is naturally cooled to the room temperature.
It is worth mentioning that in the embodiment of the present invention, the repeated sintering process is a pre-carbonization process; after the steps of dipping, drying and pre-carbonizing are carried out for a plurality of times, and finally sintering at high temperature is carried out to remove carbon to obtain the mixed metal oxide catalyst coating. The invention adopts low-temperature sintering at 250-300 ℃ to pre-carbonize the mixed sol to form carbide, inhibits the excessive growth of electrode mixed oxide particles, prevents shrinkage caused by thermal stress, inhibits crack growth, improves the surface flatness and quality of the electrode, and prolongs the service life of the electrode.
As a further aspect of the invention, there is also provided a dimensionally stable anode, prepared by the above-described preparation method.
As a further aspect of the invention, there is also provided the use of a dimensionally stable anode as described above in the field of the preparation of sterile water by electrolysis of a sodium chloride solution.
The following examples further illustrate the preparation process of dimensionally stable anodes, but are not limited to the following examples, and any equivalent changes made according to the technical scheme of the present invention are within the protection scope of the present invention.
The evaluation of the electrocatalytic activity of the anode obtained in the embodiment of the invention mainly refers to a determination method specified in the industry standard HG/T2471-2001, namely the metal anode coating of the electrolytic cell, and the comprehensive performance of the electrode such as the generation of active chlorine of the electrode is evaluated, and the chlorine evolution potential (E) is respectively determined200，Cl2) Oxygen evolution potential (E)200，O2) Chlorine evolution-oxygen evolution potential difference (Delta E)1＝E200，O2-E200，Cl2) Polarizability (. DELTA.E)2＝E200Cl2，-E20，Cl2) The parameters (subscript is electrode unit mA/cm in measurement)2Current density and type of gas evolved); electrocatalytic preparation of hypochlorous acid from anodes obtained in the examples of the inventionThe electrolytic capacity of the disinfectant is performed in a small diaphragm-free electrolytic cell; wherein, the size of the anode and the cathode is 30mm multiplied by 1.5mm multiplied by 20 mm; a cathode and an anode which are used for assembling an electrolytic cell and have the specification of 65mm multiplied by 22mm multiplied by 1 mm; the distance between the two electrodes is 20 mm; the cathode is a Pt-Ti coating; the concentration of NaCl in the electrolyte is 2 g/L-9 g/L; the hypochlorite concentration (active chlorine) in the anode region was determined by spectroscopy.
Example 1
Polishing a metal titanium sheet by 800-mesh abrasive paper, and then polishing by 2000-mesh abrasive paper; washing with ultrapure water, and soaking in acetone for degreasing; washing with acetone for 2 times, and oven drying; and then, soaking the metal titanium sheet in oxalic acid solution with the temperature of 90 ℃ to 3 percent for 2 hours, and then washing the metal titanium sheet with water for later use. TiOSO is weighed according to the molar ratio of Sn/Ru/Ti (x/(3-x)/7 (x) being 0.01) and the total concentration of the three elements (Sn + Ru + Ti) being 0.4mol/L4、RuCl3、SnCl4And adding a proper amount of pure water to dissolve to obtain a mixed metal salt precursor solution (recorded as solution A1). Preparing 0.05mol/L citric acid solution, and measuring enough citric acid solution according to the molar ratio of (Sn + Ru + Ti) to citric acid of 3: 1; weighing polyethylene glycol with molecular weight of 1000 according to the molar ratio of-COOH/-OH to 0.5 of citric acid to polyethylene glycol, and adding into citric acid solution; obtaining a mixed solution of citric acid and dihydric alcohol (marked as solution B1); uniformly mixing and stirring the solution A1 and the solution B1, and heating the mixture in an oil bath at 90 ℃ under stirring at the stirring speed of 150 rpm; after 3 hours of reaction, the reaction mixture was cooled to room temperature to give a viscous catalyst sol coating (designated as C1). Soaking the metal titanium sheet cleaned in advance in the mixed viscous sol C1 for 10min, taking out, and baking in a baking oven at 120 ℃ for 0.5 hour; and then quickly transferring the mixture into a muffle furnace at 300 ℃, quickly taking out the mixture after the sintering time is 30 minutes, and cooling the mixture to room temperature. Blowing the sintered metal titanium sheet covered with the catalyst coating clean by a blower, re-soaking in the coating C1, and repeating the soaking, drying and sintering for 10 times; and finally, after sintering for 40 minutes at 250-300 ℃, heating to 450 ℃ at the speed of 2 ℃/min, prolonging the time to 1 hour, and naturally cooling to room temperature to obtain a DSC electrode (marked as DSC-1). The obtained DSC-1 electrode and Pt-Ti-based electrode were separately used asThe anode and the cathode are assembled into an electrolytic cell; according to the determination method specified in the industry standard HG/T2471-2001, metal anode coating of electrolytic cell; measuring the chlorine evolution potential (E) of the obtained DSC electrode200，Cl2) Oxygen evolution potential (E)200，O2) Chlorine evolution-oxygen evolution potential difference (Delta E)1＝E200，O2-E200，Cl2) Polarizability (. DELTA.E)2＝E200，C12-E20，C12V) (see table 1, which is a corresponding list of parameters such as chlorine evolution potential, oxygen evolution potential, chlorine evolution-oxygen evolution potential difference, polarizability, etc. of the dimensionally stable anodes obtained in examples 1 to 6 of the present invention and comparative example 1).
Example 2
Polishing a metal titanium sheet by 800-mesh abrasive paper, and then polishing by 2000-mesh abrasive paper; washing with ultrapure water, and soaking in acetone for degreasing; washing with acetone for 3 times, and oven drying; then, the metal titanium sheet is put into oxalic acid solution with the temperature of 90 ℃ to 3 percent to be soaked for 1 hour, and then is washed clean by water for standby. TiOSO is weighed according to the molar ratio of Sn/Ru/Ti (x/(3-x)/7 (x) being 0.5) and the total concentration of the three elements (Sn + Ru + Ti) being 0.3mol/L4、RuCl3、SnCl4And adding a proper amount of pure water to dissolve to obtain a mixed metal salt precursor solution (recorded as solution A2). Preparing 0.08mol/L citric acid solution, and measuring enough citric acid solution according to the molar ratio of (Sn + Ru + Ti) to citric acid of 2: 1; weighing polyethylene glycol with molecular weight of 800 according to the molar ratio of-COOH/-OH to 0.8 of citric acid to polyethylene glycol, and adding into citric acid solution; obtaining a mixed solution of citric acid and dihydric alcohol (marked as solution B2); uniformly mixing and stirring the solution A2 and the solution B2, and heating the mixture in an oil bath at the temperature of 120 ℃ under stirring at the stirring speed of 250 rpm; after 1 hour of reaction, cooling to room temperature gave a viscous catalyst sol coating (noted as C2). Soaking a metal titanium sheet which is cleaned in advance in the mixed viscous sol C2 for 20min, taking out, and placing in a drying oven at 90 ℃ for baking for 1 hour; and then quickly transferring the mixture into a muffle furnace at 280 ℃, quickly taking out the mixture after the sintering time is 40 minutes, and cooling the mixture to room temperature. Blowing the sintered metal titanium sheet coated with the catalyst coating by using a blower, re-soaking the metal titanium sheet in the coating C2, and repeating the steps of soaking, drying and sintering according to the above steps13 times; and after the last sintering at 280 ℃ for 40 minutes, heating to 400 ℃ at the speed of 2 ℃/min, prolonging the time to 2 hours, and finally naturally cooling to room temperature to obtain the DSC electrode (marked as DSC-2). Respectively taking the obtained DSC-2 electrode and the Pt-Ti electrode as an anode and a cathode to assemble an electrolytic cell; according to the determination method specified in the industry standard HG/T2471-2001, metal anode coating of electrolytic cell; measuring the chlorine evolution potential (E) of the obtained DSC electrode200，C12) Oxygen evolution potential (E)200，O2) Chlorine evolution-oxygen evolution potential difference (Delta E)1＝E200，O2-E200，Cl2) Polarizability (. DELTA.E)2＝E200，Cl2-E20，Cl2V) etc. (see table 1).
Example 3
Polishing a metal titanium sheet by 800-mesh abrasive paper, and then polishing by 2000-mesh abrasive paper; washing with ultrapure water, and soaking in acetone for degreasing; washing with acetone for 2-3 times, and drying; then, the titanium sheet is put into oxalic acid solution with the temperature of 90 ℃ to 3 percent to be soaked for 1 hour, and then is washed clean by water for standby. TiOSO is weighed according to the molar ratio of Sn/Ru/Ti (x/(3-x)/7 (x) 1) and the total concentration of the three elements (Sn + Ru + Ti) of 0.2mol/L4、RuCl3、SnCl4And adding a proper amount of pure water to dissolve to obtain a mixed metal salt precursor solution (recorded as solution A3). Preparing 0.1mol/L citric acid solution, and measuring enough citric acid solution according to the molar ratio of (Sn + Ru + Ti) to citric acid of 1: 1; weighing glycol with the molecular weight of 600 according to the molar ratio of citric acid to polyethylene glycol-COOH/-OH ═ 1, and adding the glycol into the citric acid solution; obtaining a mixed solution of citric acid and dihydric alcohol (marked as solution B3); uniformly mixing and stirring the solution A3 and the solution B3, and heating the mixture in an oil bath at 100 ℃ under stirring at the stirring speed of 300 rpm; after 2 hours of reaction, the reaction mixture was cooled to room temperature to give a viscous catalyst sol coating (designated as C3). Soaking a metal titanium sheet which is cleaned in advance in the mixed viscous sol C3 for 15min, taking out, and placing in a drying oven at 100 ℃ for baking for 1 hour; and then quickly transferring the mixture into a muffle furnace at 250 ℃, quickly taking out the mixture after the sintering time is 50 minutes, and cooling the mixture to room temperature. Blowing the sintered metal titanium sheet covered with the catalyst coating by a blower, and re-soakingIn coating C3, the impregnation-drying-sintering was repeated 15 times as described above; and after the last sintering at 250 ℃ for 50 minutes, heating to 450 ℃ at the speed of 2 ℃/min, prolonging the time to 1 hour, and finally naturally cooling to room temperature to obtain a DSC electrode (marked as DSC-3). Assembling the obtained DSC-3 electrode and the Pt-Ti electrode as an anode and a cathode respectively to form an electrolytic cell; according to the determination method specified in the industry standard HG/T2471-2001, metal anode coating of electrolytic cell; measuring the chlorine evolution potential (E) of the obtained DSC electrode200，Cl2) Oxygen evolution potential (E)200，O2) Chlorine evolution-oxygen evolution potential difference (Delta E)1＝E200，O2-E200，Cl2) Polarizability (. DELTA.E)2＝E200，Cl2-E20，Cl2V) etc. (see table 1).
FIG. 1 is a scanning electron microscope image of a representative surface topography of a DSC anodic coating prepared in example 3 of the present invention; as shown in fig. 1, in embodiment 3 of the present invention, a high molecular polymer viscous sol is introduced to form a hydrophilic viscous mixed sol, so as to improve the high temperature sintering performance of the electrode catalytic coating; the electrode flatness is improved and the coating cracks and adhesion are greatly reduced.
Fig. 3 is a graph showing the change of the concentration of active chlorine generated in the anode region of the cell assembled by the DSC-3 electrode obtained in example 3 of the present invention with respect to electrolysis time, and as shown in fig. 3, the active chlorine is obtained by electrocatalysis of NaCl solutions of different concentrations successfully by the DSC-3 electrode prepared in example 3 of the present invention, which shows that the electrochemical performance of the dimensionally stable anode of the present invention is significantly improved when the dimensionally stable anode is used in low-concentration electrolytic sodium chloride solution.
Example 4
Polishing a metal titanium sheet by 800-mesh abrasive paper, and then polishing by 2000-mesh abrasive paper; washing with ultrapure water, and soaking in acetone for degreasing; washing with acetone for 2-3 times, and drying; then, the titanium sheet is put into oxalic acid solution with the temperature of 90 ℃ to 3 percent to be soaked for 1 hour, and then is washed clean by water for standby. TiOSO is weighed according to the molar ratio of Sn/Ru/Ti (x/(3-x)/7 (x) being 1.5) and the total concentration of the three elements (Sn + Ru + Ti) being 0.3mol/L4、RuCl3、SnCl4And adding a proper amount of pure water to dissolve to obtain a mixed metal salt precursor solution (recorded as solution A4). Fitting for mixingAdding 0.1mol/L citric acid solution, and measuring enough citric acid solution according to the molar ratio of (Sn + Ru + Ti) to citric acid of 2: 1; weighing polyethylene glycol with the molecular weight of 300 according to the molar ratio of-COOH/-OH to 0.5 of citric acid to polyethylene glycol, and adding the polyethylene glycol into the citric acid solution; obtaining a mixed solution of citric acid and dihydric alcohol (marked as solution B4); uniformly mixing and stirring the solution A4 and the solution B4, and heating the mixture in an oil bath at 90 ℃ under stirring at the stirring speed of 300 rpm; after 2 hours of reaction, the reaction mixture was cooled to room temperature to give a viscous catalyst sol coating (designated as C4). Soaking a metal titanium sheet which is cleaned in advance in the mixed viscous sol C4 for 15min, taking out, and placing in a drying oven at 100 ℃ for baking for 1 hour; and then quickly transferring the mixture into a muffle furnace at 280 ℃, quickly taking out the mixture after the sintering time is 40 minutes, and cooling the mixture to room temperature. Blowing the sintered metal titanium sheet covered with the catalyst coating clean by a blower, re-soaking in the coating C4, and repeating the soaking, drying and sintering for 13 times; and after the last sintering at 280 ℃ for 40 minutes, heating to 450 ℃ at the speed of 2 ℃/min, prolonging the time to 1 hour, and finally naturally cooling to room temperature to obtain a DSC electrode (marked as DSC-4). Assembling the obtained DSC-4 electrode and the Pt-Ti electrode as an anode and a cathode respectively to form an electrolytic cell; according to the determination method specified in the industry standard HG/T2471-2001, metal anode coating of electrolytic cell; measuring the chlorine evolution potential (E) of the obtained DSC electrode200，Cl2) Oxygen evolution potential (E)200，O2) Chlorine evolution-oxygen evolution potential difference (Delta E)1＝E200，O2-E200，Cl2) Polarizability (. DELTA.E)2＝E200，Cl2-E20，Cl2V) etc. (see table 1).
Example 5
Polishing a metal titanium sheet by 800-mesh abrasive paper, and then polishing by 2000-mesh abrasive paper; washing with ultrapure water, and soaking in acetone for degreasing; washing with acetone for 2-3 times, and drying; then, the titanium sheet is put into oxalic acid solution with the temperature of 90 ℃ to 3 percent to be soaked for 1 hour, and then is washed clean by water for standby. TiOSO is weighed according to the molar ratio of Sb/Ru/Ti (x/(3-x)/7 (x) 1) and the total concentration of the three elements (Sb + Ru + Ti) of 0.3mol/L4、RuCl3、SbCl3And adding a proper amount of pure water to dissolveAnd obtaining a mixed metal salt precursor solution (marked as solution A5). Preparing 0.1mol/L citric acid solution, and measuring enough citric acid solution according to the molar ratio of (Sb + Ru + Ti) to citric acid of 2: 1; weighing polyethylene glycol with the molecular weight of 600 according to the molar ratio of-COOH/-OH to 0.5 of citric acid to polyethylene glycol, and adding the polyethylene glycol into the citric acid solution; obtaining a mixed solution of citric acid and dihydric alcohol (marked as solution B5); uniformly mixing and stirring the solution A5 and the solution B5, and heating the mixture in an oil bath at 90 ℃ under stirring at the stirring speed of 300 rpm; after 2 hours of reaction, the reaction mixture was cooled to room temperature to give a viscous catalyst sol coating (designated as C5). Soaking a metal titanium sheet which is cleaned in advance in the mixed viscous sol C5 for 15min, taking out, and placing in a drying oven at 100 ℃ for baking for 1 hour; and then quickly transferring the mixture into a muffle furnace at 280 ℃, quickly taking out the mixture after the sintering time is 40 minutes, and cooling the mixture to room temperature. Blowing the sintered metal titanium sheet covered with the catalyst coating clean by a blower, re-soaking in the coating C5, and repeating the soaking, drying and sintering for 13 times; and after the last sintering at 280 ℃ for 40 minutes, heating to 450 ℃ at the speed of 2 ℃/min, prolonging the time to 1 hour, and finally naturally cooling to room temperature to obtain a DSC electrode (marked as DSC-5). Assembling the obtained DSC-5 electrode and the Pt-Ti series electrode as an anode and a cathode respectively to form an electrolytic cell; according to the determination method specified in the industry standard HG/T2471-2001, metal anode coating of electrolytic cell; measuring the chlorine evolution potential (E) of the obtained DSC electrode200，Cl2) Oxygen evolution potential (E)200，O2) Chlorine evolution-oxygen evolution potential difference (Delta E)1＝E200，O2-E200，Cl2) Polarizability (. DELTA.E)2＝E200，Cl2-E20，Cl2V) etc. (see table 1).
Example 6
Polishing a metal titanium sheet by 800-mesh abrasive paper, and then polishing by 2000-mesh abrasive paper; washing with ultrapure water, and soaking in acetone for degreasing; washing with acetone for 2-3 times, and drying; then, the titanium sheet is put into oxalic acid solution with the temperature of 90 ℃ to 3 percent to be soaked for 1 hour, and then is washed clean by water for standby. TiOSO is weighed according to the molar ratio of Pb/Ru/Ti (x/(3-x)/7 (x) to 1.5) and the total concentration of the three elements (Pb + Ru + Ti) is 0.3mol/L4、RuCl3、Pb(NO3)2And adding a proper amount of pure water to dissolve to obtain a mixed metal salt precursor solution (recorded as solution A6). Preparing 0.1mol/L citric acid solution, and measuring enough citric acid solution according to the molar ratio of (Pb + Ru + Ti) to citric acid of 2: 1; weighing polyethylene glycol with the molecular weight of 600 according to the molar ratio of-COOH/-OH to 0.5 of citric acid to polyethylene glycol, and adding the polyethylene glycol into the citric acid solution; obtaining a mixed solution of citric acid and dihydric alcohol (marked as solution B6); uniformly mixing and stirring the solution A6 and the solution B6, and heating the mixture in an oil bath at 90 ℃ under stirring at the stirring speed of 300 rpm; after 2 hours of reaction, the reaction mixture was cooled to room temperature to give a viscous catalyst sol coating (designated as C6). Soaking a metal titanium sheet which is cleaned in advance in the mixed viscous sol C6 for 15min, taking out, and placing in a drying oven at 100 ℃ for baking for 1 hour; and then quickly transferring the mixture into a muffle furnace at 280 ℃, quickly taking out the mixture after the sintering time is 40 minutes, and cooling the mixture to room temperature. Blowing the sintered metal titanium sheet covered with the catalyst coating clean by a blower, re-soaking in the coating C6, and repeating the soaking, drying and sintering for 13 times; and after the last sintering at 280 ℃ for 40 minutes, heating to 450 ℃ at the speed of 2 ℃/min, prolonging the time to 1 hour, and finally naturally cooling to room temperature to obtain a DSC electrode (marked as DSC-6). Assembling the obtained DSC-6 electrode and the Pt-Ti electrode as an anode and a cathode respectively to form an electrolytic cell; according to the determination method specified in the industry standard HG/T2471-2001, metal anode coating of electrolytic cell; measuring the chlorine evolution potential (E) of the obtained DSC electrode200，C12) Oxygen evolution potential (E)200，O2) Chlorine evolution-oxygen evolution potential difference (Delta E)1＝E200，O2-E200，Cl2) Polarizability (. DELTA.E)2＝E200，Cl2-E20，Cl2V) etc. (see table 1).
Comparative example 1
Polishing a metal titanium sheet by 800-mesh abrasive paper, and then polishing by 2000-mesh abrasive paper; washing with ultrapure water, and soaking in acetone for degreasing; washing with acetone for 2-3 times, and drying; then, the titanium sheet is put into oxalic acid solution with the temperature of 90 ℃ to 3 percent to be soaked for 1 hour, and then is washed clean by water for standby. According to the molar ratio of Sn/Ru/Ti (x/(3-x)/7 (x) to 1),TiOSO is respectively weighed when the total concentration of the three elements (Sn + Ru + Ti) is 0.2mol/L4、RuCl3、SnCl4And adding a proper amount of pure water to dissolve to obtain a mixed metal salt precursor solution (marked as solution R). Soaking a metal titanium sheet which is cleaned in advance in the mixed solution R for 15min, taking out, and placing in a drying oven at 100 ℃ for baking for 1 hour; and then quickly transferring the mixture into a muffle furnace at 250 ℃, quickly taking out the mixture after the sintering time is 50 minutes, and cooling the mixture to room temperature. Blowing the sintered metal titanium sheet covered with the catalyst coating clean by a blower, re-soaking in the mixed solution R, and repeating the soaking, drying and sintering for 15 times; and after the last sintering at 250 ℃ for 50 minutes, heating to 450 ℃ at the speed of 2 ℃/min, prolonging the time to 1 hour, and finally naturally cooling to room temperature to obtain a DSC electrode (marked as DSC-R). Assembling the obtained DSC-R electrode and the Pt-Ti electrode as an anode and a cathode respectively to form an electrolytic cell; according to the determination method specified in the industry standard HG/T2471-2001, metal anode coating of electrolytic cell; measuring the chlorine evolution potential (E) of the obtained DSC electrode200，Cl2) Oxygen evolution potential (E)200，O2) Chlorine evolution-oxygen evolution potential difference (Delta E)1＝E200，O2-E200，Cl2) Polarizability (. DELTA.E)2＝E200，Cl2-E20，Cl2V) etc. (see table 1).
FIG. 2 is a scanning electron micrograph of a representative surface of a coating of a DSC anode prepared in comparative example 1 of the present invention; as shown in fig. 2, the high molecular polymer hydrogel system is not formed in comparative example 1, and after the coating is sintered, the particles form an isolated island, so that the adhesive force is poor and the particles are easy to fall off; the overall flatness of the coating is poor.
Table 1: corresponding lists of chlorine evolution potential, oxygen evolution potential, chlorine evolution-oxygen evolution potential difference and polarizability parameters of dimensionally stable anodes obtained in examples 1-6 and comparative example 1 of the present invention
| E200，Cl2/V | E200，O2/V | ΔE1/V | ΔE2/V | |
| Example 1 | 1.755 | 1.932 | 0.177 | 0.253 |
| Example 2 | 1.499 | 2.073 | 0.574 | 0.127 |
| Example 3 | 1.420 | 1.843 | 0.423 | 0.074 |
| Example 4 | 1.496 | 1.704 | 0.208 | 0.142 |
| Example 5 | 1.482 | 1.853 | 0.371 | 0.131 |
| Example 6 | 1.478 | 1.812 | 0.334 | 0.126 |
| Comparative example 1 | 1.831 | 2.361 | 0.430 | 0.276 |
In conclusion, the general preparation process of the dimensionally stable anode provided by the invention is applied to the preparation of the hypochlorous acid disinfectant, and the adverse factors of cracking, easy falling and the like of an active layer of an electrolytic salt water electrode (DSC) prepared by a traditional method, which reduce the stability and the service life of the electrode, are effectively overcome. The manufacturing process comprises the following steps: brushing viscous polymer sol containing mixed metal salt with a certain composition ratio on a metal titanium plate with a purified surface; drying, transferring into a muffle furnace for pre-carbonization, cooling, coating the polymer viscous solution again, and repeating the drying and sintering processes; after coating, drying and pre-carbonizing for a plurality of times, sintering at high temperature for decarbonization to obtain the mixed metal oxide catalyst coating. The chlorine evolution potential of the obtained dimensionally stable anode can be as low as 1.42Vvs.SCE, the difference between the chlorine evolution potential and the oxygen evolution potential reaches 0.57V vs.SCE, and the polarizability is as low as 0.072V vs.SCE. The dimensionally stable anode is used for electrolyzing sodium chloride solution with low concentration, and the electrochemical performance of the dimensionally stable anode is obviously improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An electrocatalytic coating composition comprising a precursor solution of a catalytically active component and an additive; wherein:
the precursor solution of the catalytic active component comprises Ru metal salt, Ti metal salt and one of optional Sn metal salt, Pb metal salt and Sb metal salt;
the additive comprises polycarboxylic acid and polyhydric alcohol;
wherein the ratio of the polycarboxylic acid to the polyol in the additive is 0.5-1 according to the molar ratio of carboxyl to hydroxyl; and the molar ratio of the total moles of the metal elements in the precursor solution of the catalytic active component to the moles of the polycarboxylic acid is 1: 1-3: 1.
2. The electrocatalytic coating composition of claim 1, wherein said precursor solution of said catalytically active component has a molar ratio of metal elements of (Sn, Pb, or Sb)/Ru/Ti ═ x/(3-x)/7; wherein the value range of x is 0.01-1.5;
preferably, the total molar concentration of the metal elements is 0.2mol/L to 0.4 mol/L.
3. The electrocatalytic coating composition of claim 2, wherein said precursor solution of a catalytically active component comprises SnCl4、RuCl3、TiOSO4Mixed of (2) Pb (NO)3)2、RuCl3、TiOSO4Mixed or SbCl of3、RuCl3、TiOSO4And (3) mixing.
4. The electrocatalytic coating composition of claim 1, wherein said polycarboxylic acid comprises citric acid;
preferably, the concentration of the polycarboxylic acid in the additive is 0.05mol/L to 0.1 mol/L.
5. The electrocatalytic coating composition of claim 1, wherein the polyol comprises polyethylene glycol;
preferably, the polyalcohol is polyethylene glycol with the molecular weight of 300-1000.
6. A method of making a dimensionally stable anode comprising the steps of:
uniformly mixing the electrocatalytic coating composition as set forth in any one of claims 1 to 5, and performing a gelling reaction to obtain a mixed sol;
dipping a metal matrix in the mixed sol, and sintering the metal matrix dipped with the mixed gel to obtain the metal matrix containing the catalyst coating;
and repeating the dipping and sintering processes on the metal substrate containing the catalyst coating to obtain the dimensionally stable anode.
7. The method for preparing a dimensionally stable anode according to claim 6, wherein the conditions of the gelling reaction include: stirring at 90-120 deg.c and 150-400 rpm for 1-3 hr.
8. The method for preparing a dimensionally stable anode according to claim 6, wherein the dipping and sintering process is repeated 10 to 15 times;
preferably, the specific operating conditions of the sintering include: sintering at 250-300 ℃ for 30-50 minutes, and rapidly cooling to room temperature after sintering;
preferably, the temperature of the last sintering is 250-300 ℃, the sintering time is 30-50 minutes, then the temperature is raised to 400-450 ℃ at the speed of 2 ℃/min, the temperature is kept for 1-2 hours, and finally the temperature is naturally cooled to the room temperature.
9. A dimensionally stable anode, characterized by being produced by the production method according to any one of claims 6 to 8.
10. Use of a dimensionally stable anode according to claim 9 in the field of the electrolysis of sodium chloride solutions for the preparation of sterile water.
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