超支化聚合物氮修饰Pd催化剂促进甲酸电催化氧化

doi:10.7503/cjcu20190116

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (7): 1433.doi: 10.7503/cjcu20190116

超支化聚合物氮修饰Pd催化剂促进甲酸电催化氧化

于彦存^1,², 王显^1,³, 葛君杰¹, 刘长鹏¹, 邢巍¹()

1. 中国科学院长春应用化学研究所先进化学电源实验室, 长春 130022
2. 中国科学院大学, 北京 100049
3. 中国科学技术大学应用化学与工程学院, 合肥 230026

收稿日期:2019-02-25 出版日期:2019-07-10 发布日期:2019-07-09
作者简介:邢巍, 男, 博士, 研究员, 博士生导师, 主要从事化学电源与金属表面电化学处理技术研究. E-mail: xingwei@ciac.ac.cn
基金资助:
国家自然科学基金(批准号: 21633008, 21733004, 21603216)、吉林省科技发展计划项目(批准号: 20180101030JC)、中国科学院百人计划项目和外专千人计划项目(批准号: WQ20122200077)资助.

Promoted Formic Acid Electrooxidation Using PdN_x/C Catalyst Prepared with Hyperbranched Polymer^†

YU Yancun^1,², WANG Xian^1,³, GE Junjie¹, LIU Changpeng¹, XING Wei^1,^*()

1. Laboratory of Advanced Power Sources Changchun Institute of Applied Chemistry,Chinese Academy of Sciences, Changchun 130022, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. School of Applied Chemistry and Engineering,University of Science and Technology of China (USTC), Hefei 230026, China

Received:2019-02-25 Online:2019-07-10 Published:2019-07-09
Contact: XING Wei E-mail:xingwei@ciac.ac.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21633008, 21733004, 21603216.), the Jilin Province Science and Technology Development Program, China(No.20180101030JC), the Hundred Talents Program of Chinese Academy of Sciences and the Recruitment Program of Foreign Experts, China(No.WQ20122200077).

摘要/Abstract

摘要：

通过原位聚合法制备了以超支化聚合物的氮修饰的PdN_x/C催化剂, 并考察了其催化甲酸电氧化反应的性能. 采用透射电子显微镜(TEM)、 X射线光电子能谱(XPS)和X射线衍射(XRD)等技术研究了氮的引入对催化活性组分Pd的形貌及表面电子形态的影响. 结果表明, 修饰氮后Pd纳米粒子粒径可稳定在2 nm, 并且保持了较高的分散度, 改善了表面Pd电子状态. 与Pd/C催化剂相比, 氮修饰的PdN₂₀/C用于甲酸电氧化的Pd单位质量比活性提高了10.9%.

关键词: 甲酸, 燃料电池, 电氧化, 钯, 超支化聚合物

Abstract:

Nitrogen-doped PdN_x/C(x denoted as the amine-terminate and palladium molar ratio) catalyst derived from hyperbranched polymer was prepared via in-situ polymerization, and the electrocatalytic oxidation of formic acid was investigated. The morphology and surface electronic state of the catalytically active component Pd were investigated by transmission electron microscopy(TEM), high resolution transmission electron microscopy(HRTEM), X-ray photoelectron spectroscopy(XPS) and X-ray diffraction(XRD). The results indicate that the Pd nanoparticles remain an average size of 2 nm using polymer modification, and maintain high dispersion, with surface Pd mainly presenting as Pd(0). Compared with the Pd/C catalyst, the Pd unit mass specific activity of PdN₂₀/C for formic acid electrooxidation was increased by 10.9%.

Key words: Formic acid, Fuel cell, Electrooxidation, Pd, Hyperbranched polymer

中图分类号:

O646.21

TrendMD:

于彦存, 王显, 葛君杰, 刘长鹏, 邢巍. 超支化聚合物氮修饰Pd催化剂促进甲酸电催化氧化. 高等学校化学学报, 2019, 40(7): 1433.

YU Yancun, WANG Xian, GE Junjie, LIU Changpeng, XING Wei. Promoted Formic Acid Electrooxidation Using PdN_x/C Catalyst Prepared with Hyperbranched Polymer^†. Chem. J. Chinese Universities, 2019, 40(7): 1433.

图/表 7

Fig.1 XRD patterns of the PdN20/C(a) and unreduced PdN20/C(b) catalysts

Fig.2 TEM images(A―C) and size distribution histograms(D―F) of PdNx/C with different molar ratio of amine-terminate group to Pd(A, D) PdN10/C; (B, E) PdN20/C; (C, F) PdN30/C.

Fig.3 SEM image(A) and element mapping profiles(B—D) of PdN20/C (B) C; (C) N; (D) Pd.

Fig.4 XPS spectra of Pd3d(A) and N1s of PdN20/C(B)

Fig.5 CV curves for the PdNx/C catalysts in an aqueous solution of 0.5 mol/L H2SO4+0.5 mol/L HCOOH at a scan rate of 20 mV/s

Table 1 Comparison of selected N-containing monomer for formic acid electrooxidation

N-containing monomer	w(Pd)(%)		ECSA/(m²·g^-1)	Peak current/mA
N-containing monomer	Nominal	ICP	ECSA/(m²·g^-1)	Peak current/mA
AEPZ	20	21.13	205.1	506.9
ED	20	19.57	187.3	498.6
DAPD	20	20.79	196.5	464.3

Fig.6 Chronoamperometric curves at 0.2 V on the PdN20/C catalyst in an aqueous solution of 0.5 mol/L H2SO4+0.5 mol/L HCOOH

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超支化聚合物氮修饰Pd催化剂促进甲酸电催化氧化

Promoted Formic Acid Electrooxidation Using PdN_x/C Catalyst Prepared with Hyperbranched Polymer^†

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超支化聚合物氮修饰Pd催化剂促进甲酸电催化氧化

Promoted Formic Acid Electrooxidation Using PdNx/C Catalyst Prepared with Hyperbranched Polymer†

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Promoted Formic Acid Electrooxidation Using PdN_x/C Catalyst Prepared with Hyperbranched Polymer^†