CN111020675A - Preparation method of titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating - Google Patents

Preparation method of titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating Download PDF

Info

Publication number
CN111020675A
CN111020675A CN201911354065.5A CN201911354065A CN111020675A CN 111020675 A CN111020675 A CN 111020675A CN 201911354065 A CN201911354065 A CN 201911354065A CN 111020675 A CN111020675 A CN 111020675A
Authority
CN
China
Prior art keywords
titanium dioxide
dioxide nanotube
tungsten alloy
electrodeposition coating
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201911354065.5A
Other languages
Chinese (zh)
Other versions
CN111020675B (en
Inventor
周琼宇
李媛媛
王小芬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Puyang Shunkang Petroleum Engineering Technology Co ltd
Sichuan Qianyiding Technology Co ltd
Original Assignee
Foshan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Foshan University filed Critical Foshan University
Priority to CN201911354065.5A priority Critical patent/CN111020675B/en
Publication of CN111020675A publication Critical patent/CN111020675A/en
Application granted granted Critical
Publication of CN111020675B publication Critical patent/CN111020675B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • 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
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

The invention discloses a preparation method of a titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating, which comprises the following steps: a. preparing a mixed solution from cobalt sulfate, sodium tungstate, sodium sulfate, citric acid, boric acid, a titanium dioxide nanotube and a surfactant, and adjusting the pH value to 4-8 by using ammonia water; b. and performing electrodeposition on the prepared mixed solution on a copper substrate by adopting a three-electrode system to obtain the titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating. The preparation method adopts the most common electroplating method in industry, and is beneficial to industrial production; the material preparation condition requirement is low, and the operation is easy; the raw materials are low in price and easy to obtain; the electrode material has excellent precipitationHydrogen catalysis performance, hydrogen evolution test in 1M NaOH solution at 25mA/cm2The hydrogen evolution overpotential is less than 0.4V at the current density of (1).

Description

Preparation method of titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating
Technical Field
The invention relates to the technical field of electrical elements, in particular to a preparation method of a titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating.
Background
The hydrogen production by water electrolysis is an important means for realizing the industrial and cheap hydrogen preparation, but the technology has the biggest problems of large electric energy consumption, higher production cost and large electric energy consumption due to overhigh hydrogen evolution overpotential of an electrolysis electrode, so the research on reducing the hydrogen evolution overpotential to reduce the electrolysis energy consumption is particularly important. The prior electrode material for water electrolysis has the defects of high price, small specific surface, low electrocatalytic activity and the like, so that the hydrogen evolution potential of the electrolysis electrode is too high, the energy consumption is too high, and the development of the hydrogen production technology by the water electrolysis method is seriously restricted. The influence of the electrode material, especially the cathode material, on the hydrogen evolution performance is particularly important. The electrocatalytic hydrogen evolution active electrode widely used at present comprises: (1) an iron-based alloy hydrogen evolution electrode; (2) a nickel-based alloy hydrogen evolution electrode; (3) the noble metal modifies the hydrogen evolution electrode. In addition, other hydrogen evolving electrodes are: a rare earth element modified hydrogen evolution electrode, a high polymer modified hydrogen evolution electrode and the like. These materials are all used to reduce hydrogen evolution overpotential and improve catalytic performance.
Although the hydrogen evolution materials reduce hydrogen evolution overpotential to a certain extent, the materials are expensive, and the hydrogen evolution performance is still not ideal, so that the hydrogen evolution materials have certain limitations from large-scale industrial application. Therefore, the need for an electrode material which is cheap and easy to obtain and has excellent electrocatalytic performance is urgent.
Disclosure of Invention
The invention provides a preparation method of a titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating aiming at the problems, so as to solve one or more technical problems in the prior art and provide at least one beneficial choice or creation condition.
The development of nanotechnology provides a new development opportunity for the technical upgrade of traditional materials, and the nanoparticles can be used for improving the quality of the materials and the specific surface area of the materials due to the characteristics of high specific surface area, easiness in preparation and the like, so that the traditional materials have excellent catalytic performance, and the invention provides the following technical scheme:
a preparation method of a titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating comprises the following steps:
a. preparing a mixed solution from cobalt sulfate, sodium tungstate, sodium sulfate, citric acid, boric acid, a titanium dioxide nanotube and a surfactant, and adjusting the pH value to 4-8 by using ammonia water;
b. and performing electrodeposition on the prepared mixed solution on a copper substrate by adopting a three-electrode system to obtain the titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating.
Further, the concentration of the cobalt sulfate is 0.05-0.2M; the concentration of the sodium tungstate is 0.05-0.25M; the concentration of the sodium sulfate is 0.1-0.4M; the concentration of the citric acid is 0.1-0.5M; the concentration of the boric acid is 0.1-0.2M; the concentration of the titanium dioxide nanotube is 0.01-0.1M; the concentration of the surfactant is 0.01-0.1 g/l.
Further, the ammonia water concentration is 1M.
Further, the mixed solution in the step a is prepared at room temperature.
Further, the electrodeposition process in the step b is carried out under the condition of water bath at 45 ℃.
Further, the electrodeposition parameters are: current density 100mA/cm2The plating time was 1800 s.
Compared with the prior art, the invention has the advantages that:
1. the most common electroplating method in the industry is adopted, which is beneficial to industrial production;
2. the material preparation condition requirement is low, and the operation is easy;
3. the raw materials are low in price and easy to obtain;
4. the electrode material has excellent hydrogen evolution catalytic performance, and hydrogen evolution test is carried out in 1M NaOH solution at 25mA/cm2The hydrogen evolution overpotential is less than 0.4V at the current density of (1).
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples, but the present invention is not limited to these examples.
Example 1
In this embodiment, an electrolyte is first prepared: preparing a mixed solution of 0.08M cobalt sulfate, 0.09M sodium tungstate, 0.15M sodium sulfate, 0.15M citric acid, 0.13M boric acid, 0.01M titanium dioxide nanotube and 0.1g/l surfactant at room temperature, and adjusting with 1M ammonia waterPH is 4. The prepared solution is put in a water bath at 45 ℃ and a three-electrode system is adopted at 1 multiplied by 1cm2The copper substrate was subjected to electrodeposition with a current density of 100mA/cm2The plating time was 1800 s.
The obtained electrode is used as a cathode to carry out cyclic voltammetry in a 1M NaOH solution, the test temperature is 25 ℃, and the current density is 25mA/cm2When the voltage is high, the overpotential is only 0.38V.
Example 2
In this embodiment, an electrolyte is first prepared: a mixed solution of 0.08M cobalt sulfate, 0.09M sodium tungstate, 0.15M sodium sulfate, 0.15M citric acid, 0.13M boric acid, 0.05M titanium dioxide nanotubes, and 0.1g/l surfactant was prepared at room temperature, and the pH was adjusted to 4 with 1M aqueous ammonia. The prepared solution is put in a water bath at 45 ℃ and a three-electrode system is adopted at 1 multiplied by 1cm2The copper substrate was subjected to electrodeposition with a current density of 100mA/cm2The plating time was 1800 s.
The obtained electrode is used as a cathode to carry out cyclic voltammetry in a 1M NaOH solution, the test temperature is 25 ℃, and the current density is 25mA/cm2When the voltage is high, the overpotential is only 0.34V.
Example 3
In this embodiment, an electrolyte is first prepared: a mixed solution of 0.06M cobalt sulfate, 0.25M sodium tungstate, 0.15M sodium sulfate, 0.15M citric acid, 0.13M boric acid, 0.08M titanium dioxide nanotubes and 0.1g/l surfactant was prepared at room temperature, and the pH was adjusted to 4 with 1M ammonia water. The prepared solution is put in a water bath at 45 ℃ and a three-electrode system is adopted at 1 multiplied by 1cm2The copper substrate was subjected to electrodeposition with a current density of 100mA/cm2The plating time was 1800 s.
The obtained electrode is used as a cathode to carry out cyclic voltammetry in a 1M NaOH solution, the test temperature is 25 ℃, and the current density is 25mA/cm2When the voltage is higher than the threshold voltage, the overpotential is only 0.3V.
Example 4
In this embodiment, an electrolyte is first prepared: at room temperature, 0.1M of cobalt sulfate, 0.2M of sodium tungstate, 0.15M of sodium sulfate, 0.1M of citric acid, 0.15M of boric acid,A mixed solution of 0.08M titanium dioxide nanotubes and 0.1g/l surfactant was adjusted to pH 6 with 1M aqueous ammonia. The prepared solution is put in a water bath at 45 ℃ and a three-electrode system is adopted at 1 multiplied by 1cm2The copper substrate was subjected to electrodeposition with a current density of 100mA/cm2The plating time was 1800 s.
The obtained electrode is used as a cathode to carry out cyclic voltammetry in a 1M NaOH solution, the test temperature is 25 ℃, and the current density is 25mA/cm2When the voltage is high, the overpotential is only 0.36V.
The preferred embodiments of the present invention have been described in detail, but the present invention is not limited to the details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, which fall within the protective scope of the present invention.

Claims (6)

1. A preparation method of a titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating is characterized by comprising the following steps:
a. preparing a mixed solution from cobalt sulfate, sodium tungstate, sodium sulfate, citric acid, boric acid, a titanium dioxide nanotube and a surfactant, and adjusting the pH value to 4-8 by using ammonia water;
b. and performing electrodeposition on the prepared mixed solution on a copper substrate by adopting a three-electrode system to obtain the titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating.
2. The method for preparing the titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating layer according to claim 1, wherein the concentration of the cobalt sulfate is 0.05-0.2M; the concentration of the sodium tungstate is 0.05-0.25M; the concentration of the sodium sulfate is 0.1-0.4M; the concentration of the citric acid is 0.1-0.5M; the concentration of the boric acid is 0.1-0.2M; the concentration of the titanium dioxide nanotube is 0.01-0.1M; the concentration of the surfactant is 0.01-0.1 g/l.
3. The method for preparing the titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating layer according to claim 1, wherein the ammonia water concentration is 1M.
4. The method for preparing the titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating according to claim 1, wherein the mixed solution of the step a is prepared at room temperature.
5. The method for preparing the titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating according to claim 1, wherein the electrodeposition process in the step b is performed in a water bath at 45 ℃.
6. The method for preparing the titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating layer according to claim 1, wherein the electrodeposition parameters are as follows: current density 100mA/cm2The plating time was 1800 s.
CN201911354065.5A 2019-12-25 2019-12-25 Preparation method of titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating Active CN111020675B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911354065.5A CN111020675B (en) 2019-12-25 2019-12-25 Preparation method of titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911354065.5A CN111020675B (en) 2019-12-25 2019-12-25 Preparation method of titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating

Publications (2)

Publication Number Publication Date
CN111020675A true CN111020675A (en) 2020-04-17
CN111020675B CN111020675B (en) 2022-05-10

Family

ID=70214620

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911354065.5A Active CN111020675B (en) 2019-12-25 2019-12-25 Preparation method of titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating

Country Status (1)

Country Link
CN (1) CN111020675B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115074792A (en) * 2022-07-07 2022-09-20 中国计量大学 Preparation method of cobalt-based alloy film with special structure and product

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210305A (en) * 2006-12-31 2008-07-02 王为 Tungsten alloy composite plating coat material and manufacturing method thereof
CN102337569A (en) * 2011-09-19 2012-02-01 华南理工大学 Cobalt-tungsten nanometer alloy plating layer and preparation method thereof
CN105350036A (en) * 2015-10-31 2016-02-24 北京工业大学 Tungsten alloy electro-deposition method
CN105483744A (en) * 2015-11-30 2016-04-13 苏州大学 Porous hydrogen evolution catalyst, preparation method of porous hydrogen evolution catalyst and electrode containing hydrogen evolution catalyst
CN108070878A (en) * 2016-11-18 2018-05-25 中国科学院金属研究所 A kind of porous Ni-S/TiO2Compound hydrogen-precipitating electrode and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210305A (en) * 2006-12-31 2008-07-02 王为 Tungsten alloy composite plating coat material and manufacturing method thereof
CN102337569A (en) * 2011-09-19 2012-02-01 华南理工大学 Cobalt-tungsten nanometer alloy plating layer and preparation method thereof
CN105350036A (en) * 2015-10-31 2016-02-24 北京工业大学 Tungsten alloy electro-deposition method
CN105483744A (en) * 2015-11-30 2016-04-13 苏州大学 Porous hydrogen evolution catalyst, preparation method of porous hydrogen evolution catalyst and electrode containing hydrogen evolution catalyst
CN108070878A (en) * 2016-11-18 2018-05-25 中国科学院金属研究所 A kind of porous Ni-S/TiO2Compound hydrogen-precipitating electrode and preparation method thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
向翠丽等: "Ni-W-TiO2复合电极在碱性介质中的析氢电催化性能", 《化学研究与应用》 *
张雪泳 等: "钴钨合金电镀及其电催化性能的研究", 《2001年全国电子电镀年会论文集》 *
杜晶晶等: "电解水析氢电极材料的研究新进展", 《功能材料》 *
王玉等: "电沉积非晶态Co-W合金镀层在碱性溶液中的电催化析氢研", 《材料研究学报》 *
肖秀峰等: "钴钨复合电极在碱性介质中的电催化析氢性能", 《电镀与涂饰》 *
邹勇进等: "Ni-W-TiO2复合镀工艺及其镀层性能研究", 《材料保护》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115074792A (en) * 2022-07-07 2022-09-20 中国计量大学 Preparation method of cobalt-based alloy film with special structure and product
CN115074792B (en) * 2022-07-07 2024-01-16 中国计量大学 Preparation method of cobalt-based alloy film with special structure and product

Also Published As

Publication number Publication date
CN111020675B (en) 2022-05-10

Similar Documents

Publication Publication Date Title
CN109659143B (en) Nickel hydroxide/trinickel disulfide/foamed nickel compound and preparation method and application thereof
CN104846397B (en) One kind being used for electrochemical reduction CO2The electrode and its preparation method and application of formic acid processed
CN107081163B (en) Preparation and application of NiWP electrocatalyst material with three-dimensional structure
CN110205636B (en) Preparation method of self-supporting three-dimensional porous structure bifunctional catalytic electrode
CN113430553B (en) Double-function catalytic electrode based on transition metal heterogeneous layered structure and preparation method thereof
CN108554426B (en) Difunctional cobalt diselenide material and preparation and application thereof
CN107177862A (en) One kind is used for electro-catalysis and reduces CO2Prepare the electrode structure and preparation method of ethene
CN110433829B (en) MoO (MoO)2-NiSx/CC hydrogen evolution electrocatalyst and preparation method thereof
CN103422116A (en) Method for producing porous nickel-based ruthenium oxide composite hydrogen evolution electrode
WO2023143578A1 (en) Porous nickel-molybdenum-cobalt hydrogen evolution electrode, preparation method therefor and application thereof
CN110284166A (en) A kind of electro-deposition method preparing foam nickel-molybdenum alloy
CN109750317A (en) A kind of preparation method of the compound hydrogen-precipitating electrode of porous Ni-base copper rhenium
CN110314690A (en) Bimetallic sulfide Ni with heterogeneous interface coupling3S2/ FeS composite material and preparation method and application
Han et al. Study of amorphous Ni–S–Co alloy used as hydrogen evolution reaction cathode in alkaline medium
CN110404540B (en) Preparation method of hollow-out iron-selenium derivative catalyst, product and application thereof
CN106319558B (en) A kind of MoS of high-efficiency multiple2- Zn hydrogen-precipitating electrodes and preparation method thereof
CN113235125B (en) Nickel-based NiCo 2 O 4 Electrocatalyst and its use in electrocatalytic oxidation of glycerol
CN111020675B (en) Preparation method of titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating
CN108118360A (en) A kind of efficiently production formic acid Cu-Sn-Cu layered laminate foam electrodes and preparation method thereof
CN109985631B (en) Carbon-coated Janus structure metal/metal oxide composite catalyst and preparation and application thereof
CN106591926A (en) Method for preparing CNTs-porous nickel/nickel oxide hydrogen evolution reaction catalyst on surface of steel
CN114318361B (en) Preparation method of vanadium oxide modified Raney nickel alloy electrode, electrode and application
CN113249743B (en) Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof
CN108977848A (en) A kind of Cu2The preparation method of the Quito O layer photocathode thin-film material
CN114622238B (en) Preparation and application of transition metal-based hydrogen and oxygen evolution dual-functional electrode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20221129

Address after: 457000 No.39, 150m south east of the intersection of Renqiu Road and Panjin Road, Puyang City, Henan Province

Patentee after: PUYANG SHUNKANG PETROLEUM ENGINEERING TECHNOLOGY Co.,Ltd.

Address before: No. 3510, floor 35, building 1, No. 500, middle section of Tianfu Avenue, Chengdu hi tech Zone, China (Sichuan) pilot Free Trade Zone, Chengdu, Sichuan 610000

Patentee before: Sichuan qianyiding Technology Co.,Ltd.

Effective date of registration: 20221129

Address after: No. 3510, floor 35, building 1, No. 500, middle section of Tianfu Avenue, Chengdu hi tech Zone, China (Sichuan) pilot Free Trade Zone, Chengdu, Sichuan 610000

Patentee after: Sichuan qianyiding Technology Co.,Ltd.

Address before: 528000 No. 18, Jiangwan Road, Chancheng District, Guangdong, Foshan

Patentee before: FOSHAN University