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

doi:10.11949/0438-1157.20181485

Abstract

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

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

CLC Number:

O 646.541

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.

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.

Figures/Tables 9

Fig.1 Schematic illustration of preparation process of NPGC

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

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

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

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)

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)

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)

Fig.7 Schematic diagram of cathodic oxygen reduction reaction

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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