CN109518168B - 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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CN109518168B
CN109518168B CN201811536164.0A CN201811536164A CN109518168B CN 109518168 B CN109518168 B CN 109518168B CN 201811536164 A CN201811536164 A CN 201811536164A CN 109518168 B CN109518168 B CN 109518168B
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titanium
compound
ruthenium
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electrode plate
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CN109518168A (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 (1)

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、钛化合物和石墨烯分散至100mL异丙醇中，得到钌化合物、铱化合物、钛化合物和石墨烯溶液；所述钛化合物、钌化合物、铱化合物、石墨烯的质量比为20：11：3：3；
（2）将上述钌化合物、铱化合物、钛化合物和石墨烯溶液混合，得到钌化合物、铱化合物、钛化合物和石墨烯溶液混合液；
（3）将步骤（2）中得到的混合液以喷涂方式转移到钛基板上，得到涂覆后的钛基板；
（4）将步骤（3）得到涂覆后的钛基板在80℃环境中干燥；
（5）将烘干后的钛基板转移至500℃的氩气气氛的高温炉中进行退火5min；
（6）重复步骤（3）-步骤（5）15次，得到具有高催化活性的多金属催化活性钛基板；
（7）以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；
（8）将步骤（7）涂覆后电极转移至150℃氮气气氛高温炉退火5min，即得高稳涂层的活性钛基电极板；
所述的钌化合物为醋酸钌；所述的铱化合物为氯铱酸；所述的钛化合物为四氯化钛。
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