Pt-CeO2/聚苯乙烯磺酸盐功能化碳纳米管复合物的制备及对甲醇的电催化氧化性能

doi:10.7503/cjcu20170168

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (1): 157.doi: 10.7503/cjcu20170168

Pt-CeO₂/聚苯乙烯磺酸盐功能化碳纳米管复合物的制备及对甲醇的电催化氧化性能

陈晨, 李丽, 陈金华(), 张小华(), 许杰, 李益波, 韦杰

湖南大学化学化工学院, 化学生物传感与计量学国家重点实验室, 长沙 410082

收稿日期:2017-03-22 出版日期:2018-01-10 发布日期:2017-12-19
作者简介:联系人简介: 张小华, 女, 博士, 副教授, 主要从事表面处理及高分子材料研究. E-mail:mickyxie@hnu.edu.cn; 陈金华, 男, 博士, 教授, 主要从事纳米材料和电催化材料研究. E-mail:chenjinhua@hnu.cn
基金资助:
国家自然科学基金(批准号: 21475035, 21235002, 21275041)、长江学者和创新团队发展计划项目(批准号: PCSIRT)、湖南省自然科学基金(批准号:12JJ2010)、国家自然科学基金创新研究群体基金(批准号: 21521063)和湖南大学大学生创新训练项目资助

Preparation and Electrocatalytic Performance for Methanol Oxidation of Pt-CeO₂/Sodium-4-styrenesulfonate Functionalized Carbon Nanotube Composites^†

CHEN Chen, LI Li, CHEN Jinhua^*(), ZHANG Xiaohua^*(), XU Jie, LI Yibo, WEI Jie

State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China

Received:2017-03-22 Online:2018-01-10 Published:2017-12-19
Contact: CHEN Jinhua,ZHANG Xiaohua E-mail:chenjinhua@hnu.cn;mickyxie@hnu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21475035, 21235002, 21275041), the Program for Changjiang Scholars and Innovative Research Team in University, China(No.PCSIRT), the Hunan Provincial Natural Science Fund, China(No.12JJ2010), the Science Fund for Creative Research Groups of the National Natural Science Foundation of China(No.21521063) and the Students Innovation Training Program at Hunan University, China

摘要/Abstract

摘要：

通过阴离子聚合物聚苯乙烯磺酸钠(PSS)对碳纳米管(CNTs)进行非共价功能化修饰得到PSS 功能化的碳纳米管(PSS-CNTs), 利用带负电的PSS和Ce³⁺之间的静电作用将Ce³⁺组装到CNTs表面, 再利用Ce³⁺与PtC $l 4 2 -$ 之间存在的静电作用和氧化还原反应实现CeO₂和Pt纳米粒子在CNTs表面的原位沉积, 得到复合催化剂Pt-CeO₂/PSS-CNTs. 采用透射电子显微镜(TEM)、 X射线衍射仪(XRD)、能谱仪(EDS)及拉曼光谱仪(Raman)等对催化剂进行了表征. 电化学性能测试结果表明, 由于PSS-CNTs表面原位沉积的Pt纳米粒子相对于在原始CNTs上沉积的Pt纳米粒子具有更小的粒径、更好的分散均匀性和稳定性, 同时Pt与CeO₂之间存在良好的协同效应, Pt-CeO₂/PSS-CNTs催化剂对甲醇电催化氧化具有较好的催化活性和化学稳定性, 当n_Pt/n_Ce=2/3时催化性能最优.

关键词: 直接甲醇燃料电池, 功能化碳纳米管, 稀土氧化物, 电催化活性, 稳定性

Abstract:

Carbon nanotubes(CNTs) were noncovalently modified by anionic polymer poly(sodium-4-styrenesulfonate)(PSS) to obtain PSS functionalized CNTs(PSS-CNTs), and then Ce³⁺ was assembled to CNTs surface through the electrostatic interaction between electropositive Ce³⁺ and electronegative PSS. Through the electrostatic interaction and oxidation-reduction reaction between Ce³⁺and PtC $l 4 2 -$ , CeO₂ and Pt nanoparticles were in-situ deposited on the surface of CNTs to obtain PSS-CNTs supported Pt-CeO₂ composite catalyst(Pt-CeO₂/PSS-CNTs). The structure, component and micromorphology of Pt-CeO₂/PSS-CNTs were characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD), X ray photoelectron spectroscopy(XPS), energy dispersive X-ray spectroscopy(EDS) and Raman spectroscopy, respectively. The electrochemical study shows that, due to the smaller particle size, the better dispersion uniformity and stability of Pt nanoparticles in-situ deposited on the surface of PSS-CNTs compared with those on the original CNTs, and the synergetic effect between Pt and CeO₂, Pt-CeO₂/PSS-CNTs, especially Pt-CeO₂/PSS-CNTs with n_Pt/n_Ce of 2/3, exhibits higher catalytic activity and stability for methanol electrooxidation compared with Pt-CeO₂/CNTs and PtRu/C.

Key words: Direct methanol fuel cell, Functionalized carbon nanotubes, Rare earth oxide, Electrocatalytic activity, Stability

中图分类号:

O646

TrendMD:

陈晨, 李丽, 陈金华, 张小华, 许杰, 李益波, 韦杰. Pt-CeO₂/聚苯乙烯磺酸盐功能化碳纳米管复合物的制备及对甲醇的电催化氧化性能. 高等学校化学学报, 2018, 39(1): 157.

CHEN Chen, LI Li, CHEN Jinhua, ZHANG Xiaohua, XU Jie, LI Yibo, WEI Jie. Preparation and Electrocatalytic Performance for Methanol Oxidation of Pt-CeO₂/Sodium-4-styrenesulfonate Functionalized Carbon Nanotube Composites^†. Chem. J. Chinese Universities, 2018, 39(1): 157.

图/表 11

Fig.1 Raman spectra of PSS-CNTs(a) and CNTs(b)

Fig.2 XRD patterns of Pt-CeO2/PSS-CNTs(a) and Pt-CeO2/CNTs(b)

Fig.3 TEM images(A, C) and size-distribution(B, D) of Pt-CeO2/PSS-CNTs(A, B) and Pt-CeO2/CNTs(C, D)Inset of (A): HRTEM image of Pt-CeO2/PSS-CNTs.

Fig.4 XPS spectra of Pt(A), Ce(B), C(C) and survey XPS spectrum(D) of Pt-CeO2/CNTs(nPt/nCe=2/3) v, u: Ce(Ⅲ); v'″, u'″: Ce(Ⅳ); v″,u″: satellite peak.

Fig.5 XPS spectra of Pt(A), Ce(B), C(C) and survey XPS spectrum(D) of Pt-CeO2/PSS-CNTs(nPt/nCe=2/3) v, u: Ce(Ⅲ); v'″, u'″: Ce(Ⅳ); v″,u″: satellite peak.

Table 1 Content of Pt and Ce in Pt-CeO2/PSS-CNTs with different nPt/nCe

Theoretical ratio of n_Pt/n_Ce	Molar fraction(%)		Experimental ratio of n_Pt/n_Ce
Theoretical ratio of n_Pt/n_Ce	Pt		Ce
2/1	1.94	1.04	1.87/1
2/2	1.78	1.87	1.90/2
2/3	1.89	2.82	2.01/3
2/4	1.73	3.31	2.09/4

Fig.6 Cyclic voltammograms of Pt-CeO2/PSS-CNTs with nPt/nCe ratio of 2/1(a), 2/2(b), 2/3(c) and 2/4(d) in 0.5 mol/L H2SO4+1.0 mol/L CH3OH solution at a scan rate of 50 mV/s

Fig.7 Cyclic voltammograms of the Pt-CeO2/PSS-CNTs(a), Pt-CeO2/CNTs(b) and PtRu/C(c) catalysts in 0.5 mol/L H2SO4+1.0 mol/L CH3OH solution at a scan rate of 50 mV/s

Fig.8 Cyclic voltammograms of the Pt-CeO2/PSS-CNTs(a), Pt-CeO2/CNTs(b) and PtRu/C(c)catalysts in 0.5 mol/L H2SO4 solution at a scan rate of 50 mV/s

Fig.9 Long-term cycle stability of the Pt-CeO2/PSS-CNTs(a), Pt-CeO2/CNTs(b) and PtRu/C(c) catalysts in 0.5 mol/L H2SO4+1.0 mol/L CH3OH solution

Fig.10 i-t curves of Pt-CeO2/PSS-CNTs(a), Pt-CeO2/CNTs(b) and PtRu/C(c) catalysts in 0.5 mol/L H2SO4+1.0 mol/L CH3OH solution at 0.6 V

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Pt-CeO₂/聚苯乙烯磺酸盐功能化碳纳米管复合物的制备及对甲醇的电催化氧化性能

Preparation and Electrocatalytic Performance for Methanol Oxidation of Pt-CeO₂/Sodium-4-styrenesulfonate Functionalized Carbon Nanotube Composites^†

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