CN109518168A - 一种高稳涂层的活性钛基电极板的制备方法 - Google Patents

一种高稳涂层的活性钛基电极板的制备方法 Download PDF

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CN109518168A
CN109518168A CN201811536164.0A CN201811536164A CN109518168A CN 109518168 A CN109518168 A CN 109518168A CN 201811536164 A CN201811536164 A CN 201811536164A CN 109518168 A CN109518168 A CN 109518168A
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titanium
compound
electrode plate
ruthenium
active
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CN109518168B (zh
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刘新亮
王双飞
覃程荣
聂双喜
姚双全
梁辰
刘杨
王志伟
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Guangxi University
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Abstract

本发明属于电化学技术领域，具体涉及的是一种高稳涂层的活性钛基电极板的制备方法。本发明以钛为基材，以多元金属催化层，以致密氧化物为保护层的高稳活性钛基阳极材料；所述多元金属催化层是利用热解法形成钛基催化层主体；所述致密氧化物保护层为结合溶胶‑凝胶法和电化学沉积法形成致密钛基保护层。本发明制备的高稳涂层的活性钛基电极板具有电催化活性高、寿命长、涂层致密不易脱落、活性位点多的优点，可用于氯碱工业，造纸工业、污水处理等领域。

Description

一种高稳涂层的活性钛基电极板的制备方法
技术领域
本发明属于电化学技术领域，具体涉及的是一种高稳涂层的活性钛基电极板的制备方法。
背景技术
涂覆钛基电极板是以钛或钛合金为基体，利用Ru、Sn、Mn、Ir、V、Ta、Nb等活性元素的金属氧化物对其表面进行涂覆处理，其具有电化学稳定性好，催化效率高，析氧电位高、析氯电位低等优点。涂覆钛基阳极板可以根据电极的不同用途和要求，有针对性的调整电极的涂层配方和设计涂层结构，以此来降低副反应的发生，提高目标产物的产率和电流效率。这种高稳活性钛基阳极板可广泛用于氯碱工业，造纸工业、污水处理等领域。
涂覆钛基电极板的制备方法包括热分解法、溶胶-凝胶法、电化学沉积法等方法。根据电极的不同用途和要求，利用热分解法、溶胶-凝胶法、电化学沉积法等不同方法设计不同结构的涂覆钛基阳极板，其活性不同、稳定性不同。
涂覆钛基电极板涂层制备方法多样，工艺简单，活性高，但其寿命较短，基材易钝化、涂层易发生龟裂脱落。
发明内容
本发明的目的在于提供一种融合热分解法、溶胶-凝胶法、电化学沉积法的涂层制备技术的高稳涂层的活性钛基阳极制备方法。利用本发明制备的高稳涂层的活性钛基阳极板具有电催化活性高、寿命长、涂层致密不易脱落、活性位点多的优点。
为解决涂覆钛基电极板的技术问题，本发明提出的技术方案如下：
一种高稳涂层的活性钛基电极板的制备方法，包括如下步骤：
(1)分别将钌化合物、铱化合物、钛化合物和锰化合物分散至的含浓盐酸的异丙醇或异丙醇中，得到钌化合物、铱化合物、钛化合物和锰化合物溶液；
(2)将上述钌化合物、铱化合物、钛化合物和锰化合物溶液在30-50℃，按一定比例混合，得到钌化合物、铱化合物、钛化合物和锰化合物溶液混合液；
(3)将步骤(2)中得到的混合液以刷涂方式或喷涂方式转移到电极板上，得到涂覆后的电极板；
(4)将步骤(3)得到涂覆后的电极板烘干；
(5)将烘干后的电极板进行退火煅烧固载；
(6)重复步骤(3)-步骤(5)数次，得到涂覆钛钌铱锰活性催化电极板；
(7)将钌、铱、石墨烯通过溶胶-凝胶法和电化学沉积法涂覆到涂层表面；
(8)将步骤(7)涂覆后电极转移至氮气气氛高温炉退火，即得高稳涂层的活性钛基电极板。
作为优选，所述的钌化合物为醋酸钌、氧化钌或三氯化钌；所述的铱化合物为二氧化铱、氯铱酸或四氯化铱；所述的钛化合物为四氯化钛；所述的锰化合物为高锰酸钾。
作为优选，步骤(1)中钌化合物、铱化合物、钛化合物和锰化合物溶液混合液中钌：铱：钛：锰元素的质量比为0.1-3：0.2-1：1-6：0.1-0.5。
作为优选，步骤(4)中烘干的温度为80-90℃。
作为优选，步骤(5)中所述退火煅烧温度为300-700℃。
作为优选，步骤(8)中所述退火煅烧温度为150-200℃。
与现有技术相比，本发明具有的有益效果为：
本发明以钛为基材，以多元金属催化层，以致密氧化物为保护层制备的高稳活性钛基阳极材料；所述多元金属催化层是利用热解法形成钛基催化层主体；所述致密氧化物保护层为结合溶胶-凝胶法和电化学沉积法形成致密钛基保护层。本发明制备的高稳涂层的活性钛基电极板具有电催化活性高、寿命长、涂层致密不易脱落、活性位点多的优点，可用于氯碱工业，造纸工业、污水处理等领域。
附图说明
图1为本发明的高稳涂层的活性钛基电极板的结构示意图；
图2为本发明的高稳涂层的活性钛基电极板的伏安循环曲线；
有关附图标记的说明：
1-钛基板；2-多元金属活性催化涂层；3-致密金属氧化物致密氧化物保护层。
具体实施方式
实施例1
如图1所示，一种高稳涂层的活性钛基电极板，包括：钛基板1、多元金属活性催化涂层2和致密金属氧化物致密氧化物保护层3。
所述的高稳涂层的活性钛基电极板的制备方法，包括如下步骤：
(1)先将钛基板经过喷砂抛光，去油和酸腐蚀；
(2)分别将四氯化钛、醋酸钌、氯铱酸、石墨烯分散在100ml异丙醇中，利用喷涂技术将混合液依次转移至钛基板上；所述的四氯化钛、醋酸钌、氯铱酸、石墨烯的质量比为20:11:3:3
(3)将涂覆后的钛基板在80℃环境中干燥，然后转移至500℃的氩气气氛的高温炉中退火5min；
(4)重复步骤(2)-步骤(3)15次，获得具有高催化活性的多金属催化活性钛基板；
(5)将上述步骤(4)制备的多金属催化活性钛基板为阴极，石墨电极为阳极，以RuCl3为前驱体，控制电流3mA/cm2，同时滴加NaOH，电沉积150min，在热解的龟裂缝中形成水和氧化钌保护层；
(6)将上述步骤(5)制备的水和氧化钌多金属催化活性钛基板转移到150℃氮气气氛高温炉退火5min，即制备得到高稳活性钛基电极板。
实施例2
如图1所示，一种高稳涂层的活性钛基电极板，包括：钛基板1、多元金属活性催化涂层2和致密金属氧化物致密氧化物保护层3。
所述的高稳涂层的活性钛基电极板的制备方法，包括如下步骤：
(1)先将钛基板经过喷砂抛光，去油和酸腐蚀；
(2)以RuCl3为前驱体，分散在盐酸的乙醇溶液中，经过陈化、预热，同时滴加NaOH，得到电解液；
(3)以钛基板为阳极，铂为辅助电极，电沉积250min，控制电流9mA/cm2，沉积形成水和氧化钌钛基板。
(4)分别将四氯化钛、三氯化钌、氧化石墨烯分散在异丙醇中，利用刷涂技术将混合液依次转移至步骤(3)中制得的水和氧化钌钛基板上；所述的四氯化钛、三氯化钌、氧化石墨烯的质量比为20:11:5
(5)将涂覆后的钛基板在90℃环境中干燥，然后转移至550℃的氩气气氛的高温炉中退火20min；
(6)重复步骤(4)-(5)20次，得到多金属催化活性氧化钌钛基板；
(7)以RuCl3为前驱液，滴入沸腾的盐酸溶液中，分离，制得氧化钌胶体溶液；
(8)将上述步骤(6)制备的多金属催化活性氧化钌钛基板浸渍于步骤(7)中制备的氧化钌胶体液中，获得胶体填充的多金属催化活性氧化钌钛基板；
(9)将上述步骤(8)制备的水和氧化钌多金属催化活性钛基板转移到200℃氮气气氛高温炉退火10min，即得到高稳涂层的活性钛基电极板。
实施例3
如图1所示，一种高稳涂层的活性钛基电极板，包括：钛基板1、多元金属活性催化涂层2和致密金属氧化物致密氧化物保护层3。
所述的高稳涂层的活性钛基电极板的制备方法，包括如下步骤：
(1)先将钛基板经过喷砂抛光，去油和酸腐蚀；
(2)分别将二氧化钛、五氧化二钒、三氯化钌、四氯化铱分散在100ml异丙醇中，利用喷涂技术将混合液依次转移至钛基板上；二氧化钛、五氧化二钒、三氯化钌、四氯化铱的质量比3:1:1:4
(3)将涂覆后的钛基板在85℃环境中干燥，然后转移至400℃的氩气气氛的高温炉中退火10min；
(4)重复步骤(2)-(3)17次；获得具有高催化活性的多金属催化活性钛基板；
(5)以RuCl3为前驱液，滴入沸腾的盐酸溶液中，分离，制得氧化钌胶体溶液；
(6)将上述步骤(4)制备的多金属催化活性氧化钌钛基板浸渍于(5)制备的氧化钌胶体液与石墨烯混合液中，获得胶体填充的多金属催化活性氧化钌钛基板；
(7)将上述步骤(6)制备的水和氧化钌多金属催化活性钛基板转移到160℃氮气气氛高温炉退火6in，即得到高稳活性钛基电极板。
如图2所示，伏安曲线比较平滑，无氧化还原峰。正向扫描出现析氧反应拐点，析氧电位约为1.25V/SCE。电压在-0.2-1.2V内，无析氧或吸氢反应。

Claims (6)

1.一种高稳涂层的活性钛基电极板的制备方法，其特征在于，包括如下步骤：
(1)分别将钌化合物、铱化合物、钛化合物和锰化合物分散至的含浓盐酸的异丙醇或异丙醇中，得到钌化合物、铱化合物、钛化合物和锰化合物溶液；
(2)将上述钌化合物、铱化合物、钛化合物和锰化合物溶液在30-50℃，按一定比例混合，得到钌化合物、铱化合物、钛化合物和锰化合物溶液混合液；
(3)将步骤(2)中得到的混合液以刷涂方式或喷涂方式转移到电极板上，得到涂覆后的电极板；
(4)将步骤(3)得到涂覆后的电极板烘干；
(5)将烘干后的电极板进行退火煅烧固载；
(6)重复步骤(3)-步骤(5)数次，得到涂覆钛钌铱锰活性催化电极板；
(7)将钌、铱、石墨烯通过溶胶-凝胶法和电化学沉积法涂覆到涂层表面；
(8)将步骤(7)涂覆后电极转移至氮气气氛高温炉退火，即得高稳涂层的活性钛基电极板。
2.根据权利要求1所述的高稳涂层的活性钛基电极板的制备方法，其特征在于，所述的钌化合物为醋酸钌、氧化钌或三氯化钌；所述的铱化合物为二氧化铱、氯铱酸或四氯化铱；所述的钛化合物为四氯化钛；所述的锰化合物为高锰酸钾。
3.根据权利要求1所述的高稳涂层的活性钛基电极板的制备方法，其特征在于，步骤(1)中钌化合物、铱化合物、钛化合物和锰化合物溶液混合液中钌：铱：钛：锰元素的质量比为0.1-3：0.2-1：1-6：0.1-0.5。
4.根据权利要求1所述的高稳涂层的活性钛基电极板的制备方法，其特征在于，步骤(4)中烘干的温度为80-90℃。
5.根据权利要求1所述的高稳涂层的活性钛基电极板的制备方法，其特征在于，步骤(5)中所述退火煅烧温度为300-700℃。
6.根据权利要求1所述的高稳涂层的活性钛基电极板的制备方法，其特征在于，步骤(8)中所述退火煅烧温度为150-200℃。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113699548A (zh) * 2021-08-25 2021-11-26 北京化工大学 弱酸盐层保护的析氧催化电极及其制备与用途、及提高析氧催化电极析氧反应稳定性的方法
CN114134346A (zh) * 2021-11-30 2022-03-04 大连理工大学 一种连续离子膜脱钠-沉钒的方法
CN114405794A (zh) * 2022-01-19 2022-04-29 西安西热水务环保有限公司 一种连续电除盐膜块钛电极涂层的制备方法
CN114438541A (zh) * 2020-10-19 2022-05-06 蓝星(北京)化工机械有限公司 含石墨烯析氯阳极

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN113881960A (zh) * 2021-09-30 2022-01-04 西安建筑科技大学 一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4189358A (en) * 1978-07-14 1980-02-19 The International Nickel Company, Inc. Electrodeposition of ruthenium-iridium alloy
JPH04191398A (ja) * 1990-11-26 1992-07-09 Nippon Steel Corp 不溶性電極
CN1118384A (zh) * 1994-09-08 1996-03-13 广州有色金属研究院 电解冶金工业用涂层电极
US20080149476A1 (en) * 2006-05-09 2008-06-26 Daiki Ataka Engineering Co., Ltd. Anode for electrochemical reaction
RU2385969C1 (ru) * 2008-08-06 2010-04-10 Общество с ограниченной ответственностью научно-производственное предприятие "ЭКОФЕС" Способ получения электрода для электрохимических процессов
CN101894675A (zh) * 2010-07-19 2010-11-24 南昌航空大学 一种钛基超级电容器薄膜电极的制作方法
CN101922016A (zh) * 2009-06-09 2010-12-22 明达实业(厦门)有限公司 一种用于氯发生器的钛电极及其制备方法
CN107829109A (zh) * 2017-10-20 2018-03-23 上海同臣环保有限公司 一种钛基二氧化铱涂层电极及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3711385A (en) * 1970-09-25 1973-01-16 Chemnor Corp Electrode having platinum metal oxide coating thereon,and method of use thereof
CA1225066A (en) * 1980-08-18 1987-08-04 Jean M. Hinden Electrode with surface film of oxide of valve metal incorporating platinum group metal or oxide
IL73536A (en) * 1984-09-13 1987-12-20 Eltech Systems Corp Composite catalytic material particularly for electrolysis electrodes,its manufacture and its use in electrolysis
DE102010043085A1 (de) * 2010-10-28 2012-05-03 Bayer Materialscience Aktiengesellschaft Elektrode für die elektrolytische Chlorherstellung

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4189358A (en) * 1978-07-14 1980-02-19 The International Nickel Company, Inc. Electrodeposition of ruthenium-iridium alloy
JPH04191398A (ja) * 1990-11-26 1992-07-09 Nippon Steel Corp 不溶性電極
CN1118384A (zh) * 1994-09-08 1996-03-13 广州有色金属研究院 电解冶金工业用涂层电极
US20080149476A1 (en) * 2006-05-09 2008-06-26 Daiki Ataka Engineering Co., Ltd. Anode for electrochemical reaction
RU2385969C1 (ru) * 2008-08-06 2010-04-10 Общество с ограниченной ответственностью научно-производственное предприятие "ЭКОФЕС" Способ получения электрода для электрохимических процессов
CN101922016A (zh) * 2009-06-09 2010-12-22 明达实业(厦门)有限公司 一种用于氯发生器的钛电极及其制备方法
CN101894675A (zh) * 2010-07-19 2010-11-24 南昌航空大学 一种钛基超级电容器薄膜电极的制作方法
CN107829109A (zh) * 2017-10-20 2018-03-23 上海同臣环保有限公司 一种钛基二氧化铱涂层电极及其制备方法

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
V.PANIC ET AL.: ""The properties of carbon-supported hydrous ruthenium oxide obtained from RuOxHy sol"", 《ELECTROCHIMICA ACTA》 *
刘文武等: ""两种DSA电极的制备及其对有机废水降解的电催化性能"", 《环境化学》 *
姚颖悟等: ""钛基锡锑氧化物涂层电极的研究进展"", 《电镀与涂饰》 *
宋诗稳等: ""稀土金属-氧化石墨烯-PbO2/SnO2-Sb/Ti型稳阳极的制备及性能研究—钇、钕、铒、镧、镨"", 《中国环境科学学会科学技术年会论文集》 *
张瑞峰等: ""钌-钛金属氧化物涂层电极的电子能谱分析"", 《分析化学》 *
王海荣等: ""Ru/RGO改性DSA电极处理酸性橙II模拟废水的实验研究"", 《河南教育学院院报（自然科学版）》 *
王玲利等: ""钛基氧化物Ru(0.4-x)IrxTi0.6电极电化学性能研究"", 《电化学》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114438541A (zh) * 2020-10-19 2022-05-06 蓝星(北京)化工机械有限公司 含石墨烯析氯阳极
CN114438541B (zh) * 2020-10-19 2024-04-09 蓝星(北京)化工机械有限公司 含石墨烯析氯阳极
CN113699548A (zh) * 2021-08-25 2021-11-26 北京化工大学 弱酸盐层保护的析氧催化电极及其制备与用途、及提高析氧催化电极析氧反应稳定性的方法
CN114134346A (zh) * 2021-11-30 2022-03-04 大连理工大学 一种连续离子膜脱钠-沉钒的方法
CN114134346B (zh) * 2021-11-30 2022-08-12 大连理工大学 一种连续离子膜脱钠-沉钒的方法
CN114405794A (zh) * 2022-01-19 2022-04-29 西安西热水务环保有限公司 一种连续电除盐膜块钛电极涂层的制备方法

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