氮掺杂石墨烯/多孔碳复合材料的制备及其氧还原催化性能

doi:10.11949/0438-1157.20181485

化工学报 ›› 2019, Vol. 70 ›› Issue (6): 2308-2315.DOI: 10.11949/0438-1157.20181485

• 材料化学工程与纳米技术 • 上一篇下一篇

氮掺杂石墨烯/多孔碳复合材料的制备及其氧还原催化性能

贺新福^1,²(),龙雪颖¹,吴红菊¹,张凯博¹,周均¹,李可可¹,张亚婷^1,²(),邱介山^3,⁴

1. 西安科技大学化学与化工学院，陕西西安 710054
2. 国土资源部煤炭资源勘查与综合利用重点实验室，陕西西安 710054
3. 大连理工大学化工学院，辽宁大连 116024
4. 北京化工大学化学工程学院，北京 100029

收稿日期:2018-12-17 修回日期:2019-03-19 出版日期:2019-06-05 发布日期:2019-06-05
通讯作者: 张亚婷
作者简介:<named-content content-type="corresp-name">贺新福</named-content>（1983—），男，博士，副教授，<email>hexinfu@126.com</email>
基金资助:
国家自然科学基金项目(U1703251，U1810113);陕西省重点研发计划项目(2017ZDCXL-GY-10-01-02)

Synthesis of N-doped graphene/porous carbon composite and its electrocatalytic performance on oxygen reduction reaction

Xinfu HE^1,²(),Xueying LONG¹,Hongju WU¹,Kaibo ZHANG¹,Jun ZHOU¹,Keke LI¹,Yating ZHANG^1,²(),Jieshan QIU^3,⁴

1. School of Chemistry and Chemical Engineering, Xi’an University of Science and Technology, Xi’an 710054, Shaanxi, China
2. Key Laboratory of Coal Resources Exploration and Comprehensive Utilization, Ministry of Land and Resources, Xi’an 710054, Shaanxi, China
3. School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
4. School of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2018-12-17 Revised:2019-03-19 Online:2019-06-05 Published:2019-06-05
Contact: Yating ZHANG

摘要/Abstract

摘要：

采用简单、无模板的方法制备了氮掺杂多孔石墨烯/碳复合材料(NPGC)。采用SEM、XRD、Raman、XPS等分析手段对NPGC的形貌、组成以及结构进行了表征，利用旋转圆盘电极技术测试了其电催化氧还原反应(ORR)活性。结果表明，葡萄糖在水热后生成的碳与石墨烯成功复合，并在950℃炭化、活化后形成了相互渗透、结构良好的三维片状多孔网络结构；其氮含量高达9.47%。NPGC作为一种高效的非金属ORR电催化剂，在碱性溶液中具有较高的起始电位[0.87 V(vs RHE)]和较大的极限电流密度(4.7 mA?cm^?2)，以及其ORR平均转移电子数为3.8。与商业Pt/C催化剂相比，NPGC具有较强的耐甲醇性和长期耐久性，且制备成本较低，具有广阔的应用前景。

关键词: 氧还原反应, 石墨烯, 纳米材料, 多孔碳, 电化学

Abstract:

Nitrogen-doped porous graphene/carbon composites(NPGC) were prepared by a simple and template free method.Its morphology, composition and structure were characterized by SEM, XRD, Raman and XPS. The electrocatalytic performance of NPGC on oxygen reduction reaction(ORR) was measured by a rotating disk electrode. The results showed that porous carbon generated by hydrothermal treatment of glucose was successfully compounded with graphene. After carbonization and activation at 950℃, a three-dimensional lamellar porous network structure with good permeability and structure was formed. The N content of NPGC is as high as 9.47%. NPGC showed relatively high initial potential [0.87 V(vs RHE)] and limiting current density (4.7 mA?cm^?2) for ORR in KOH solution, and the average number of ORR transferred electrons was 3.8. Compared with commercial Pt/C electrocatalyst, NPGC showed high methanol tolerance and long-term durability, and had the advantage of low preparation cost, which has broad application prospects in industry.

Key words: oxygen reduction reaction, graphene, nanomaterials, porous carbon, electrochemistry

中图分类号:

O 646.541

贺新福, 龙雪颖, 吴红菊, 张凯博, 周均, 李可可, 张亚婷, 邱介山. 氮掺杂石墨烯/多孔碳复合材料的制备及其氧还原催化性能[J]. 化工学报, 2019, 70(6): 2308-2315.

Xinfu HE, Xueying LONG, Hongju WU, Kaibo ZHANG, Jun ZHOU, Keke LI, Yating ZHANG, Jieshan QIU. Synthesis of N-doped graphene/porous carbon composite and its electrocatalytic performance on oxygen reduction reaction[J]. CIESC Journal, 2019, 70(6): 2308-2315.

图/表 9

图1 NPGC的制备过程

Fig.1 Schematic illustration of preparation process of NPGC

表1 水热反应前后GO和石墨烯/碳复合材料的质量

Table 1 Mass of GO and graphene/carbon composites before and after hydrothermal reaction

Reactants	Mass before hydrothermal reaction/mg	Mass after hydrothermal reaction/mg
GO	20	13
GO+glucose	20+800	67

图2 GO(a)、GC(b)、NPGC(c)的SEM图和NPGC的元素映射图(d)

Fig.2 SEM images of GO (a), GC (b) and NPGC (c) and element mapping images of NPGC (d)

图3 样品的XRD谱图(a)和拉曼光谱图(b)

Fig.3 XRD patterns (a) and Raman spectra (b) of samples

图4 样品的XPS全谱图(a)；氮掺杂碳材料中三种类型N原子 (b)；样品的高分辨N 1s XPS谱图(c)；样品的氮含量分析(d)

Fig.4 XPS spectra of samples (a); schematic of three types of N in N-doped carbon material (b); high-resolution N 1s spectra of samples (c); N content of samples (d)

图5 样品的循环伏安曲线(a)和线性扫描伏安(LSV)曲线(b)

Fig.5 CV curves of samples in O2-saturated 0.1 mol?L?1 KOH at a scan rate of 50 mV?s?1 (a); LSV curves of samples and Pt/C in O2-saturated 0.1 mol?L?1 KOH at a scan rate of 10 mV?s?1 and a rotating speed of 1600 r?min?1(b)

图6 NPGC的线性扫描伏安曲线(a)和在不同电压下的K-L曲线(b)

Fig.6 LSV curves of NPGC in O2-saturated 0.1 mol?L?1 KOH with different rotating speed at a scan rate of 10 mV?s?1 (a); Koutecky-Levich plots of NPGC at different potentials (b)

图7 阴极氧还原反应

Fig.7 Schematic diagram of cathodic oxygen reduction reaction

图8 NPGC和Pt/C的计时电流法曲线(a)和抗甲醇曲线(b)

Fig.8 I-t chronoamperometric curves of NPGC and Pt/C catalysts (a); methanol tolerance curves of NPGC and Pt/C by chronoamperometric response plus 3.0 mol?L?1 CH3OH for around 400 s (b)

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氮掺杂石墨烯/多孔碳复合材料的制备及其氧还原催化性能

Synthesis of N-doped graphene/porous carbon composite and its electrocatalytic performance on oxygen reduction reaction

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