CN111146461A - 一种纸-石墨-PANI-Pt电极的制备方法及其在催化H2O2电还原反应中的应用 - Google Patents

一种纸-石墨-PANI-Pt电极的制备方法及其在催化H2O2电还原反应中的应用 Download PDF

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CN111146461A
CN111146461A CN201911420661.9A CN201911420661A CN111146461A CN 111146461 A CN111146461 A CN 111146461A CN 201911420661 A CN201911420661 A CN 201911420661A CN 111146461 A CN111146461 A CN 111146461A
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张栋铭
刘有智
王浩宇
崔灿
程宇玲
袁志国
焦纬洲
祁贵生
刘志伟
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Abstract

本发明公开一种纸‑石墨‑PANI‑Pt电极的制备方法及其在催化H2O2电还原反应中的应用。制法为：（1）用铅笔在滤纸表面均匀涂绘，在其表面覆盖导电石墨层；（2）将涂有石墨层的滤纸作为工作电极，石墨棒作为对电极，氯化银电极作为参比电极，使用循环伏安法进行电沉积，制备纸‑石墨‑PANI电极；（3）将纸‑石墨‑PANI电极在H2PtCl6·6H2O溶液中静置，得到纸‑石墨‑PANI‑Pt电极。本发明制备方法简单，且无需使用有机粘结剂，所制备电极具有优异的电催化活性、耐腐蚀性、机械稳定性，用于催化过氧化氢电还原，解决了H2O2电还原性能低、电极材料稳定性差的问题，具有广泛的应用前景。

Description

一种纸-石墨-PANI-Pt电极的制备方法及其在催化H2O2电还原 反应中的应用
技术领域
本发明属于电极材料制备领域，具体涉及到一种纸-石墨-PANI-Pt电极材料的制备方法，用于催化H2O2的电还原反应。
背景技术
能源对于人类社会的生存和发展是必不可少，但是传统的化石能源面临资源匮乏和环境污染两个重要的问题，为此人们不断寻找清洁的能源来代替传统能源。燃料电池是一种将燃料和氧化剂中的化学能直接转变为电能的装置，其发电效率高、噪音低、对环境污染小，逐渐被人们所关注，为解决能源问题提供新的方向。
H2O2作为氧化剂在燃料电池中已经被广泛应用，例如直接硼氢化物-过氧化氢燃料电池、甲醇-过氧化氢燃料电池、尿素-过氧化氢燃料电池等。H2O2有很多突出优势：（1）常温下表现为液态，储存运输方便；（2）其电还原为两电子反应，需要的活化能较低；（3）价格低廉，容易获得。制备对H2O2具有高电还原催化活性的电极材料对装配高性能燃料电池非常重要。
纸在我们的生活中随处可见，近年来纸作为柔性电极材料备受关注（可参阅Dongming Zhang, Dianxue Cao, Ke Ye*, Jinling Yin, Kui Cheng, Guiling Wang*.Cobalt nano-sheet supported on graphite modified paper as a binder freeelectrode for peroxide electrooxidation[J]. Electrochimica Acta. 2014; 139:250-255.及Dongming Zhang, Ke Ye, Dianxue Cao, Jinling Yin, Kui Cheng, BinWang, Yang Xu, Guiling Wang*. Catalytic behavior of a palladium doped binderfree paper based cobalt electrode in electroreduction of hydrogen peroxide[J]. Journal of Power Sources. 2015; 273: 1142-1147.）。纸作为电极支撑体，具有价格低廉、机械性能良好、可再生、环保无污染等优点。但是其作为电极材料支撑体也存在一些问题，如：化学稳定性较差、导电性不佳等。
发明内容
本发明旨在提供一种纸-石墨-PANI-Pt电极材料的制备方法，解决了H2O2电还原性能低、电极材料稳定性差的问题。
本发明是采用电沉积法在涂有石墨层的滤纸上沉积PANI，然后通过氧化还原反应在其表面负载Pt催化剂，用于催化H2O2电还原。本发明用铅笔涂覆滤纸，在滤纸表面形成导电石墨层，C6H7N单体通过电化学聚合过程在石墨纸表面形成PANI层，还原态的PANI与H2PtCl6·6H2O发生氧化还原反应，负载Pt催化剂。本发明制备方法简单，且无需使用有机粘结剂，所制备电极具有优异的电催化活性、耐腐蚀性、机械稳定性，解决了H2O2电还原性能低、电极材料稳定性差的问题，具有广泛的应用前景。
本发明提供了一种纸-石墨-PANI-Pt电极的制备方法，包括以下步骤：
（1）用铅笔在滤纸表面均匀涂绘，在其表面覆盖导电石墨层。
（2）将涂有石墨层的滤纸作为工作电极，石墨棒作为对电极，氯化银电极作为参比电极，在H2SO4和C6H7N的混合电沉积液中，采用传统的三电极体系，使用循环伏安法进行电沉积过程，制备纸-石墨-PANI电极；循环伏安法扫描速度为50 mV·s-1，扫描范围为-0.4~1.0 V；
（3）将纸-石墨-PANI电极在H2PtCl6·6H2O溶液中静置，得到纸-石墨-PANI-Pt电极。
对上述方案作出以下进一步地说明：
步骤（2）中电沉积液组成为0.1~2.0 mol·L-1 H2SO4、0.1~0.5 mol·L-1 C6H7N，循环伏安沉积圈数为10~100圈。
步骤（3）中H2PtCl6·6H2O浓度为5 mmol·L-1，静置时间为1~16 h。
本发明提供了采用上述制备方法制得的纸-石墨-PANI-Pt电极。
本发明提供了上述纸-石墨-PANI-Pt电极在催化H2O2电还原反应中的应用。
具体应用过程为：将纸-石墨-PANI-Pt电极作为工作电极，石墨棒作为对电极，氯化银电极作为参比电极，采用常规的三电极体系，使用循环伏安法催化H2O2电还原；循环伏安法扫描范围为-0.20~0.60 V，扫描速度为10 mV·s-1，测试溶液为0.1~2.0 mol·L-1H2SO4和0.01~2.0 mol·L-1 H2O2。
本发明的有益效果：
本发明采用纸作为电极材料支撑体，廉价易得、机械性能良好、可降解、环保无污染；在其表面负载PANI使电极具有更强的化学稳定性和导电性，通过自发氧化还原反应负载Pt催化剂，简单易操作；电极材料制备过程中不使用有机粘结剂，使所制备电极材料具有良好的导电性和稳定性。
附图说明
图1为实施例1和实施例2制备的纸-石墨-PANI-Pt电极的循环伏安曲线图。
具体实施方式
下面通过实施例来进一步说明本发明，但不局限于以下实施例。
实施例1：
用铅笔在滤纸表面均匀涂绘，在其表面覆盖导电石墨层，将其剪为10 mm×10 mm的正方形片作为工作电极，石墨棒作为对电极，氯化银电极作为参比电极，在H2SO4和C6H7N的混合溶液中，采用传统的三电极体系，使用循环伏安法进行电沉积过程，制备纸-石墨-PANI电极。扫描速度为50 mV·s-1，扫描范围为-0.4~1.0 V。其电沉积液组成为2.0 mol·L-1 H2SO4和0.4 mol·L-1 C6H7N，循环伏安沉积圈数为80圈。最后将纸-石墨-PANI电极在5 mmol·L-1的H2PtCl6·6H2O溶液中静置1 h，得到纸-石墨-PANI-Pt电极。将纸-石墨-PANI-Pt电极作为工作电极，石墨棒作为对电极，氯化银电极作为参比电极，采用循环伏安法对催化H2O2电还原性能进行测试。在1.0 mol·L-1 H2SO4和1.0 mol·L-1 H2O2溶液中，当扫描速度为10 mV·s-1，电位为-0.2 V时，还原电流密度达到195.2 mA·cm-2。
实施例2：
用铅笔在滤纸表面均匀涂绘，在其表面覆盖导电石墨层，将其剪为10 mm×10 mm的正方形片作为工作电极，石墨棒作为对电极，氯化银电极作为参比电极，在H2SO4和C6H7N的混合溶液中，采用传统的三电极体系，使用循环伏安法进行电沉积过程，制备纸-石墨-PANI电极。扫描速度为50 mV·s-1，扫描范围为-0.4~1.0 V。其电沉积液组成为2.0 mol·L-1H2SO4、0.4 mol·L-1 C6H7N，循环伏安沉积圈数为80圈。最后将纸-石墨-PANI电极在5mmol·L-1 的H2PtCl6·6H2O溶液中静置4 h，得到纸-石墨-PANI-Pt电极。将纸-石墨-PANI-Pt电极作为工作电极，石墨棒作为对电极，氯化银电极作为参比电极，采用循环伏安法对催化H2O2电还原性能进行测试。在1.0 mol·L-1 H2SO4和1.0 mol·L-1 H2O2溶液中，当扫描速度为10 mV·s-1，电位为-0.2 V时，还原电流密度达到235.8 mA·cm-2。
图1示出了本发明制备的纸-石墨-PANI电极在H2PtCl6·6H2O溶液中分别静置1 h（曲线a对应实施例1）和4 h（曲线b对应实施例2）所制备的纸-石墨-PANI-Pt电极的循环伏安曲线。从图中可以看出，静置4 h所制备的纸-石墨-PANI-Pt电极催化H2O2电还原产生的电流密度更高，说明了静置时间的延长加强了所制备电极对H2O2电还原反应的催化活性。

Claims (9)

1.一种纸-石墨-PANI-Pt电极的制备方法，其特征在于包括以下步骤：
（1）用铅笔在滤纸表面均匀涂绘，在其表面覆盖导电石墨层；
（2）将涂有石墨层的滤纸作为工作电极，石墨棒作为对电极，氯化银电极作为参比电极，在H2SO4和C6H7N的混合电沉积液中，采用传统的三电极体系，使用循环伏安法进行电沉积过程，制备纸-石墨-PANI电极；
（3）将纸-石墨-PANI电极在H2PtCl6·6H2O溶液中静置，得到纸-石墨-PANI-Pt电极。
2.根据权利要求1所述的纸-石墨-PANI-Pt电极的制备方法，其特征在于：步骤（2）电沉积液中H2SO4的浓度为0.1~2.0 mol·L-1。
3.根据权利要求1所述的纸-石墨-PANI-Pt电极的制备方法，其特征在于：步骤（2）电沉积液中C6H7N的浓度为0.1~0.5 mol·L-1。
4.根据权利要求1所述的纸-石墨-PANI-Pt电极的制备方法，其特征在于：步骤（2）中扫描速度为50 mV·s-1，扫描范围为-0.4~1.0 V。
5.根据权利要求1所述的纸-石墨-PANI-Pt电极的制备方法，其特征在于：步骤（2）中循环伏安沉积圈数为10~100圈。
6.根据权利要求1所述的纸-石墨-PANI-Pt电极的制备方法，其特征在于：步骤（3）中H2PtCl6·6H2O浓度为5 mmol·L-1，静置时间为1~16 h。
7.一种权利要求1~6任一项所述的制备方法制得的纸-石墨-PANI-Pt电极。
8.一种权利要求7所述的纸-石墨-PANI-Pt电极在催化H2O2电还原反应中的应用。
9.根据权利要求8所述的应用，其特征在于：将纸-石墨-PANI-Pt电极作为工作电极，石墨棒作为对电极，氯化银电极作为参比电极，采用常规的三电极体系，使用循环伏安法催化H2O2电还原；循环伏安法扫描范围为-0.20~0.60 V，扫描速度为10 mV·s-1，测试溶液为0.1~2.0 mol·L-1 H2SO4和0.01~2.0 mol·L-1 H2O2。
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