CN116876044A - Titanium matrix manganese dioxide-based mixed oxide anode and preparation method thereof - Google Patents
Titanium matrix manganese dioxide-based mixed oxide anode and preparation method thereof Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000010936 titanium Substances 0.000 title claims abstract description 58
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000011159 matrix material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011572 manganese Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000000694 effects Effects 0.000 claims abstract description 21
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 230000033228 biological regulation Effects 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 239000003792 electrolyte Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 230000002195 synergetic effect Effects 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910006913 SnSb Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000005488 sandblasting Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 230000001680 brushing effect Effects 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241001085205 Prenanthella exigua Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- -1 Ir/Ru Substances 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical compound [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a titanium matrix manganese dioxide-based mixed oxide anode and a preparation method thereof, wherein a high corrosion-resistant intermediate layer and a manganese dioxide-based mixed coating are prepared by selecting proper matrix pretreatment and adopting a thermal decomposition method, and the anode is prepared by comprehensively utilizing the technologies of component and preparation process adjustment, anti-disproportionation treatment, surface reconstruction and the like to realize the regulation and control of the electrocatalytic activity and stability of the anode. The titanium matrix manganese dioxide-based mixed oxide anode has the advantages of high activity, long service life, simple operation, low cost, strong controllability, energy conservation, consumption reduction, easy industrialization and the like, and meanwhile, as the anode does not contain Pb, the pollution problem of Pb in anolyte and metal products is solved, and the low-cost high-performance oxide coating anode which can be used for industrial electrolysis/electrodepositing of copper, electrodeposited zinc, electrolytic manganese and the like is obtained.
Description
Technical Field
The invention relates to a preparation method of an insoluble anode material for high-performance low-cost oxygen evolution, in particular to a titanium matrix manganese dioxide-based mixed oxide anode and a preparation method thereof, which are particularly suitable for acidic oxygen evolution environments of industrial electrolysis/electro-deposition copper, electro-deposition zinc, electrolytic manganese and the like, and belong to the technical field of new materials.
Background
The existing electrolytic/electro-deposition production of copper, zinc and manganese has the problems of low electric efficiency, high energy consumption, environmental protection caused by the disposal of anode mud waste residue and the like. This is mainly due to (1) high concentration of H 2 SO 4 Pb-Ag base alloy is always adopted as an electrolytic anode in an electrolyte system, and the oxygen evolution overpotential is high; (2) The Pb-Ag based alloy anode has high density, low strength and short circuit caused by easy bending creep, reduces current efficiency and further increases energy consumption; (3) PbO of Pb-Ag base alloy anode 2 The passivation film is loose and porous, is easy to fall off to form anode mud, pollutes cathode products, and reduces product quality. Therefore, to thoroughly solve these problems in the electrolytic/electrodepositing industries of copper, zinc and manganese, there is a need to develop new lead-free, efficient, low cost oxygen evolution insoluble anodes.
It is currently best to coat Ir (iridium) oxide or mixed oxide thereof (such as IrO) on titanium substrate in acidic oxygen evolution state 2 +Ta 2 O 5 Anode, etc.), the anode has excellent electrocatalytic activity and service life, does not produce secondary pollution, and is widely applied to electrochemical industry. With the rapid development of industry, the demand for rare and noble metal Ir is increasing, so that the world Ir is less and less, the price is rapidly increased, and the industrial cost is greatly increased. Therefore, the development of the novel high-efficiency low-cost acid oxygen-evolving insoluble anode is an important scientific research and achievement application direction in the current electrochemical engineering field.
The use of low cost transition metal (Fe, co, ni, mn, sn etc.) oxides, sulfides, selenides, borides, phosphides, etc. as oxygen evolution insoluble anodes has been widely studied, and electrocatalytic activity in alkaline media is comparable to or even higher than noble metal oxides, but stability of oxygen evolution reactions in acidic media still hardly meets the electrochemical engineering service requirements. Rutile MnO 2 The catalyst has the advantages of low price, abundant resources, environmental friendliness and the like, has certain electrocatalytic activity and stability as an acidic medium oxygen evolution electrocatalyst, and is considered as one of the most likely materials to replace rare noble metal oxides. However, mnO 2 The disproportionation reaction (manganese dissolution) at the oxygen evolution potential in an acidic medium, which itself has poor conductivity, leads to a high oxygen evolution overpotential and a lower level of clothingService life.
Research shows that with the increase of the potential of the acid oxygen evolution reaction, mnO 2 Near surface Mn 3+ The concentration of the intermediate state increases rapidly, and a large number of disproportionation reactions lead to structural collapse and irreversible phase change. The MnO is increased by the electrochemical anti-disproportionation reaction of G.Nocera and the like 2 Mn of (2) 3+ Concentration by lowering Mn 3+ Coordination number realizes Mn 3+ In regular tetrahedron (MnO) 4 ) Is fixed in the furnace, improve MnO 2 Electrochemical stability of the acid oxygen evolution reaction. Simulation and experiments by using I.E.L.Stephens et al prove that the high oxygen evolution potential in the acidic medium>1.7vs RHE) by replacing MnO with Ti 2 (120) The soluble Mn on the crystal face step regulates the energy of the crystal face step, and effectively inhibits the dissolution of manganese. J.Zhou and S.Q.Liang et al report a potassium ion stable alpha-form K with oxygen defects 0.8 Mn 8 O 16 For Zn/MnO 2 The battery, research shows that K+ ion is stably embedded into K 0.8 Mn 8 O 16 Can enhance the intrinsic stability of the material in the tunnel holes.
To improve MnO 2 The conductive performance and electrocatalytic activity of the anode, researchers have generally adopted several approaches to solve this problem, namely, nanocrystallization of anode coating materials, rapid increase of electrocatalytic active sites, decrease of MnO 2 Interface contact resistance with current collector and reduction of electron/ion transport distance, e.g. MnO 2 Highly uniformly dispersed and deposited on a current collector (comprising carbon nanotube arrays, graphene, metal nanowire arrays and the like) with a nano structure; secondly, other types of high-conductivity materials (such as Ir/Ru, silver nanowires, high-conductivity graphene and the like) are mixed, so that MnO is improved 2 The electric conductivity of the body and the addition of oxygen evolution active sites achieve a synergistic effect; third, defect/strain engineering by forming a composite material on MnO 2 The defects of oxygen vacancies, lattice distortion and the like are increased, the carrier concentration is improved, and the oxygen evolution reaction activity of active sites is improved; fourth, metal ions (such as Mo, co, W, V, fe) are doped into MnO by chemical or electrochemical method 2 Improvement of MnO in bulk lattice 2 The conductivity of the body also plays a role in synergistic catalysis, such as that taught by Habazaki, university of North seaThe validity of this technical approach was confirmed by prior work in the eye group.
There are many methods for preparing the anode coated with the titanium matrix oxide, such as thermal decomposition, sol-gel, chemical complexation, hot dipping, electrodeposition, etc. From the present research, the thermal decomposition method is the most commonly used method for preparing the anode of the titanium matrix oxide coating in the supply industry, and has the advantages of good stability of the anode coating, simple operation, low cost, strong controllability, easy industrialization and the like. Therefore, the invention obtains the low-cost high-performance oxide coating electrode for electrolytic/electrodeposited copper, electrodeposited zinc, electrolytic manganese and the like by adjusting the components and the preparation process of rutile manganese dioxide, the anti-disproportionation treatment, the surface reconstruction and other means.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a titanium matrix manganese dioxide-based mixed oxide anode and a preparation method thereof, and the components and preparation process, surface modification, anti-disproportionation treatment, surface reconstruction and other means of manganese dioxide are adjusted to obtain a required mixed oxide coating structure, which has excellent electrocatalytic performance and stability. Compared with the existing sol-gel method, chemical complexation method and the like, the preparation method for preparing the titanium matrix manganese dioxide-based mixed oxide anode by adopting the thermal decomposition method has the advantages of simple preparation, low cost and long service life. The low-cost high-performance oxide coating anode material prepared by the preparation method is used for replacing the rare and noble IrO widely used at present 2 A toxic Pb alloy anode.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
the preparation method of the titanium matrix manganese dioxide-based mixed oxide anode comprises the following steps: a protective interlayer is prepared by selecting proper matrix pretreatment and then adopting a thermal decomposition method to prevent oxidation and corrosion of the matrix, wherein the interlayer is doped with oxides such as F, sb and In 2 Preferably SbO 2 +SnO 2 An intermediate layer; finally, the method obtains excellent electrocatalytic activity and stability through means of regulation and control of an oxide component and a preparation process, anti-disproportionation treatment, surface reconstruction and the likeA coating of a manganese mixed oxide of a titanium matrix.
The method specifically comprises the following steps:
1) Pretreatment of a matrix: pretreatment of the substrate has a great influence on the stability and electrocatalytic activity of the coating. And (3) repeatedly washing the pure titanium (TA 1 or TA 2) plate with deionized water after sand blasting, alkali washing, oil removing, acid washing and etching, and finally drying for use.
2) An intermediate layer: preparing SnCl 4 +SbCl 3 Wherein the atomic molar ratio of Sn to Sb is (0.5-2): (0.1-1), and the total metal ion molar concentration is 0.1-0.3M. The coating liquid is uniformly coated on the surface of a titanium substrate by a brush, baked and sintered for 10min at 200-700 ℃, repeatedly coated for 1-3 times, and finally sintered for 30-80 min at 200-700 ℃ to obtain a uniform SnSb oxide layer.
3) Preparing a manganese dioxide-based mixed oxide coating: preparation of Mn (NO) 3 ) 2 Mn 2+ The molar concentration is 0.5-3.0M. The prepared coating liquid is brushed on the titanium-based intermediate layer, dried for 5-20 min at 70-150 ℃, sintered for 8-25 min at 250-550 ℃, the steps are repeated, 10-30 layers are coated, and finally sintered for 0.5-3 h at 300-650 ℃ for the first time, thus obtaining the manganese dioxide-based mixed oxide coating of the titanium matrix.
4) Performing anti-disproportionation treatment: an electrochemical induced anti-disproportionation reaction method is adopted at 0.5M H 2 SO 4 Mn is realized in the electrolyte through the regulation and control of the scanning voltage (-1.5V vs. RHE) range 3+ And stabilizing the electrochemical capture in the center of a regular tetrahedron, inhibiting the dissolution of manganese in the anodic acid oxygen evolution process and improving the electrocatalytic activity of the manganese.
5) Surface reconstruction: the self-reconstruction of the anode surface by metal ions in the electrolyte was carried out at 0.5. 0.5M H 2 SO 4 Adding 0.1-0.5M Mn into electrolyte 2+ 、0.05～0.1M Cu 2+ 、0.05～0.3M Fe 2+ 、0.01～0.1M Co 2+ 、0.03～0.2M Zn 2+ Plasma is circularly scanned at 0.8-2.0V vs. RHE, and the self-reconstruction of the anode surface is realized through the interaction between metal ions in electrolyte and the anode surface, so that the electrocatalytic activity of the anode is enhancedStability.
Further, in the step 3), co (NO 3) 2, fe (NO 3) 3, ni (NO 3) 2, agNO3, NH4ReO4, etc. are doped in a small amount, so as to obtain a synergistic catalytic metal such as Co, fe, ni, ag, re, etc. in the coating;
further, in the step 3), the contents of Co (NO 3) 2, fe (NO 3) 3, ni (NO 3) 2, agNO3 and NH4ReO4 in the mixed coating liquid are respectively 0.01-0.05M, 0.01-0.06M, 0.02-0.1M, 0.01-0.08M and 0.005-0.06M, so as to achieve the aim of synergistic catalytic enhancement activity;
further, the step 3) is to dope a small amount of Ti (OCH) 2 CH 2 CH 2 CH 3 ) 4 、TaCl 5 、CaCO 3 、SrCO 3 KCl, naCl, etc., so as to obtain Ti, ta, ca, sr, K, na, etc. synergistically stable metals in the coating, so as to achieve the purpose of improving stability by solidifying active atoms;
further, the step 3) is performed by Ti (OCH) 2 CH 2 CH 2 CH 3 ) 4 、TaCl 5 、CaCO 3 、SrCO 3 The content of KCl and NaCl in the mixed coating liquid is 0.005-0.1M, 0.001-0.03M, 0.02-0.08M, 0.001-0.05M, 0.005-0.02M and 0.005-0.02M respectively;
stabilization of Mn by addition of synergistic catalysis (e.g., co, fe, ni, ag, etc.) and synergistic stabilization 3+ Alloying elements (such as Ti, ta, ca, sr, K, na and the like) to realize the enhancement of the electrocatalytic activity and stability of the anodic acid oxygen evolution reaction.
The manganese dioxide-based mixed oxide anode of the titanium matrix prepared by the method is 0.5 to 0.5M H 2 SO 4 10-2000 mA cm in solution ～2 At current density, its oxygen evolution overpotential is very stable, compared with the traditional IrO 2 The Ti electrode stability is close.
The invention has the following beneficial effects: the anode material of the manganese dioxide-based oxide coating of the titanium matrix solves the problems of MnO through means of component and preparation process regulation, anti-disproportionation treatment, surface reconstruction and the like 2 Low oxygen evolution reaction activity and poor stability. Novel developed titanium matrix manganese dioxide-based oxide coatingThe layered anode has the advantages of high electrocatalytic activity, long service life, energy saving, consumption reduction, simple preparation process and the like, and meanwhile, as the anode does not contain Pb, the pollution problem of Pb in anolyte and metal products is solved.
Detailed Description
Example 1
Pretreatment of a titanium matrix: the pure titanium plate after sand blasting is used as a matrix, and is etched in an oxalic acid solution of 20wt.% at 90 ℃ for 10min after alkali cleaning and oil removal, so that the surface of a sample is bright white, and finally, the sample is washed clean and dried by deionized water.
An intermediate layer: preparing SnCl 4 +SbCl 3 The mixed solution has an atomic molar ratio of Sn to Sb of 0.5:0.1 and a total metal ion molar concentration of 0.01M. The coating liquid is uniformly coated on the surface of a titanium matrix by a hairbrush, baked and sintered for 10min at 300 ℃, repeatedly coated for 3 times, and finally sintered for 30min at 200 ℃ to generate a uniform SnSb oxide layer.
Manganese dioxide-based mixed oxide coating: configuration Mn (NO) 3 ) 2 Mn 2+ The molar concentration is 0.5M, the doping content of the synergic catalysis doping components Co (NO 3) 2, fe (NO 3) 3, ni (NO 3) 2, agNO3 and NH4ReO4 in the mixed coating liquid is 0.05M, 0.06M, 0.1M, 0.08M and 0.06M respectively, and the synergic stable doping components Ti (OCH) 2 CH 2 CH 2 CH 3 ) 4 、TaCl 5 、CaCO 3 、SrCO 3 The doping contents of KCl and NaCl in the mixed coating liquid are respectively 0.005M, 0.001M, 0.02M, 0.001M, 0.005M and 0.005M. And brushing the prepared coating liquid on the titanium-based intermediate layer, drying for 5min at 70 ℃, sintering for 8min at 250 ℃, repeating the steps, coating 10 layers, and finally sintering for 1h at 250 ℃ to obtain the manganese dioxide-based mixed oxide coating of the titanium substrate.
Performing anti-disproportionation treatment: mn is realized by adopting an electrochemical induction anti-disproportionation reaction method and regulating and controlling the scanning voltage (-1.5V vs. RHE) range 3+ And stabilizing the electrochemical capture in the center of a regular tetrahedron, inhibiting the dissolution of manganese in the anodic acid oxygen evolution process and improving the electrocatalytic activity of the manganese.
Surface reconstruction:the surface of the anode subjected to the anti-disproportionation treatment is further subjected to self-reconstruction by metal ions in the electrolyte, and the electrolyte is prepared at a temperature of 0.5M H 2 SO 4 Addition of 0.1M Mn to electrolyte 2+ 、0.05M Cu 2+ 、0.05M Fe 2+ 、0.01M Co 2+ 、0.03M Zn 2+ The plasma is circularly scanned for more than 200 times at 0.8-2.0V vs. RHE, so as to realize the self-reconstruction of the surface of the anode and enhance the electrocatalytic activity and stability of the anode.
Example 2
Pretreatment of a titanium matrix: the pure titanium plate after sand blasting is used as a matrix, and is etched in an oxalic acid solution of 20wt.% at 80 ℃ for 30min after alkali cleaning and oil removal, so that the surface of a sample is bright white, and finally, the sample is washed clean and dried by deionized water.
An intermediate layer: preparing SnCl 4 +SbCl 3 The mixed solution had an atomic molar ratio of Sn to Sb of 2:1 and a total metal ion molar concentration of 0.03M. The coating liquid is uniformly coated on the surface of a titanium substrate by a brush, baked and sintered for 10min at 700 ℃, repeatedly coated for 3 times, and finally sintered for 80min at 700 ℃ to generate a uniform SnSb oxide layer.
Manganese dioxide-based mixed oxide coating: configuration Mn (NO) 3 ) 2 Mn 2+ The molar concentration is 3.0M, the doping content of the synergic catalysis doping components Co (NO 3) 2, fe (NO 3) 3, ni (NO 3) 2, agNO3 and NH4ReO4 in the mixed coating liquid is 0.05M, 0.06M, 0.1M, 0.08M and 0.06M respectively, and the synergic stable doping components Ti (OCH) 2 CH 2 CH 2 CH 3 ) 4 、TaCl 5 、CaCO 3 、SrCO 3 The doping contents of KCl and NaCl in the mixed coating liquid are respectively 0.1M, 0.03M, 0.08M, 0.05M, 0.02M and 0.02M. And brushing the prepared coating liquid on the titanium-based intermediate layer, drying for 20min at 150 ℃, sintering for 25min at 550 ℃, repeating the steps, coating 30 layers, and finally sintering for 3h at 650 ℃ to obtain the manganese dioxide-based mixed oxide coating of the titanium matrix.
Performing anti-disproportionation treatment: mn is realized by adopting an electrochemical induction anti-disproportionation reaction method and regulating and controlling the scanning voltage (-1.5V vs. RHE) range 3+ Is captured electrochemically and is then processedStable in the center of regular tetrahedron, inhibit the dissolution of Mn in the process of acid oxygen evolution of anode and promote its electrocatalytic activity.
Surface reconstruction: the surface of the anode subjected to the anti-disproportionation treatment is further subjected to self-reconstruction by metal ions in the electrolyte, and the electrolyte is prepared at a temperature of 0.5M H 2 SO 4 Addition of 0.5M Mn to electrolyte 2+ 、0.1M Cu 2+ 、0.3M Fe 2+ 、0.1M Co 2+ 、0.2M Zn 2+ The plasma is circularly scanned for more than 200 times at 0.8-2.0V vs. RHE, so as to realize the self-reconstruction of the surface of the anode and enhance the electrocatalytic activity and stability of the anode.
TABLE 1 titanium matrix manganese dioxide based oxide anode Performance
The oxygen evolution potential of this example was tested using a conventional three electrode system, with the anode electrode being the working electrode, the Saturated Calomel Electrode (SCE) as the reference electrode, and the platinum sheet electrode as the auxiliary electrode. The oxygen evolution potential of the manganese dioxide-based mixed oxide coated electrode of the titanium substrate was measured using a model M352 software using a Potentiostat/Galva nostat M273 tester manufactured by EG & GPAR under a scan rate of 0.5mV s-1 at 25 ℃. The accelerated life test electrolyte is 0.5M H2SO4 solution, the temperature is 50 ℃, a pure titanium plate is used as a cathode, the prepared electrode is an anode, the distance between the plates is 1cm, and the current density of the accelerated life test is 2A cm < -2 >. The accumulated electrolysis time when the cell voltage is increased by 5V from the initial value is defined as the accelerated life of the electrode by adopting a double-circuit voltage stabilizing direct current power supply, and a certain amount of distilled water and H2SO4 are added irregularly during the electrolysis process to maintain the liquid level and concentration of the electrolyte. The electrolysis time and the voltage value of the electrolytic tank are recorded at regular intervals. The experimental results are shown in Table 1, and the oxygen evolution overpotential of the titanium matrix manganese dioxide-based oxide coated anode is very stable and is close to the stability of the traditional IrO2/Ti electrode.
Claims (6)
1. A preparation method of a titanium matrix manganese dioxide-based mixed oxide anode is characterized by comprising the following steps: the method comprises the following steps:
1) Pretreatment of a matrix: sequentially carrying out sand blasting, alkali washing, oil removal, acid washing and etching on the pure titanium plate, repeatedly washing the pure titanium plate with deionized water, and finally drying the pure titanium plate for use;
2) An intermediate layer: preparing SnCl 4 +SbCl 3 (0.5-2), the total metal ion molar concentration is 0.1-0.3M, uniformly brushing the coating liquid on the surface of a titanium substrate by using a brush, sintering for 10min at 200-700 ℃ after drying, repeatedly coating for 1-3 times, and finally sintering for 30-80 min at 200-700 ℃ to obtain a uniform SnSb oxide layer;
3) Preparing a manganese dioxide-based mixed oxide coating: preparation of Mn (NO) 3 ) 2 Mn 2+ The molar concentration is 0.5-3.0M, the prepared coating liquid is brushed on the titanium-based intermediate layer, dried for 5-20 min at 70-150 ℃, sintered for 8-25 min at 250-550 ℃, the steps are repeated, 10-30 layers are coated, and finally sintered for 0.5-3 h at 300-650 ℃ for the first time, so as to obtain the manganese dioxide-based mixed oxide coating of the titanium substrate;
4) Performing anti-disproportionation treatment: an electrochemical induced anti-disproportionation reaction method is adopted at 0.5M H 2 SO 4 Mn is realized in the electrolyte through the regulation and control of the scanning voltage (-1.5V vs. RHE) range 3+ The electrochemical capture of the anode is stabilized in the center of a regular tetrahedron, so that the dissolution of manganese in the anode acid oxygen evolution process is inhibited and the electrocatalytic activity of the manganese is improved;
5) Surface reconstruction: the self-reconstruction of the anode surface by metal ions in the electrolyte was carried out at 0.5. 0.5M H 2 SO 4 Adding 0.1-0.5M Mn into electrolyte 2+ 、0.05～0.1M Cu 2+ 、0.05～0.3M Fe 2+ 、0.01～0.1M Co 2+ 、0.03～0.2M Zn 2+ Plasma is circularly scanned at 0.8-2.0V vs. RHE, and the self-reconstruction of the anode surface is realized through the interaction between metal ions in the electrolyte and the anode surface.
2. The method for preparing a titanium matrix manganese dioxide-based mixed oxide anode according to claim 1, which is characterized in that: in the step 3), a small amount of Co (NO 3) 2, fe (NO 3) 3, ni (NO 3) 2, agNO3, NH4ReO4 and the like are doped so as to obtain Co, fe, ni, ag, re and other synergistic catalytic metals in the coating.
3. The method for preparing a titanium matrix manganese dioxide-based mixed oxide anode according to claim 1, which is characterized in that: in step 3) a small amount of doped Ti (OCH) 2 CH 2 CH 2 CH 3 ) 4 、TaCl 5 、CaCO 3 、SrCO 3 KCl, naCl, etc., so as to obtain Ti, ta, ca, sr, K, na, etc. synergistically stable metals in the coating to achieve the purpose of curing reactive atoms to improve stability.
4. The method for preparing a titanium matrix manganese dioxide-based mixed oxide anode according to claim 2, wherein the method comprises the following steps: in the step 3), the contents of Co (NO 3) 2, fe (NO 3) 3, ni (NO 3) 2, agNO3 and NH4ReO4 in the mixed coating liquid are respectively 0.01-0.05M, 0.01-0.06M, 0.02-0.1M, 0.01-0.08M and 0.005-0.06M, so as to achieve the aim of synergistic catalytic enhancement activity.
5. A method for preparing a titanium matrix manganese dioxide-based mixed oxide anode according to claim 3, wherein: said step 3) is Ti (OCH) 2 CH 2 CH 2 CH 3 ) 4 、TaCl 5 、CaCO 3 、SrCO 3 The content of KCl and NaCl in the mixed coating liquid is 0.005-0.1M, 0.001-0.03M, 0.02-0.08M, 0.001-0.05M, 0.005-0.02M and 0.005-0.02M respectively.
6. A titanium matrix manganese dioxide based mixed oxide anode characterized by: the method of any one of claims 1-5, wherein the titanium-based manganese dioxide-based mixed oxide anode is prepared.
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