钴/氮掺杂碳纳米管/石墨烯复合材料的构筑及氧还原催化性能

doi:10.7503/cjcu20170288

摘要/Abstract

摘要：

以石墨烯/N-甲基吡咯烷酮(NMP)分散体和Co(NO₃)₂混合物为前驱体, 经过高温和化学掺杂处理, 制备了钴/氮掺杂的碳纳米管/石墨烯复合材料(Co/N-CNT/Gr-X, X代表煅烧温度), 并对其进行物相表征和电化学性能测试. 结果表明, 在钴盐催化下, 石墨烯分散体中的有机溶剂NMP成为碳源, 在石墨烯表面形成高密度的碳纳米管, 形成了三维多级结构; 同时, 钴离子部分氧化成为氧化物, 部分与N形成Co—N活性位点, 其协同作用极大改善了催化剂的氧还原性能. 其中Co/N-CNT/Gr-800的还原峰电位为-0.137 V(vs. SCE), 极限电流密度为4.24 mA/cm², 电子转移数为3.34, 表现出优异的耐甲醇中毒能力.

关键词: 电催化剂, 氧还原反应, 碳纳米管, 石墨烯, 杂原子掺杂

Abstract:

Cobalt/nitrogen co-doped carbon nanotube/graphene composites(Co/N-CNT/Gr-X, X represents the calcination temperature) were prepared by high temperature nitrogen doping with homemade graphene/N-methylpyrrolidone(NMP) dispersion and Co(NO₃)₂ as precursors. The results show that the solvent NMP in the graphene dispersion as a carbon source forms high-density carbon nanotubes on the surface of graphene with cobalt salt as catalysts, which provided a three-dimensional porous structure favorable for massive transfer of electrolyte ions. In addition, some cobalt ions were oxidized to form cobalt oxide and the others reacted with N to form a Co—N active site, thus leading to a markedly enhanced oxygen reduction reaction(ORR) performance. Among them, Co/N-CNT/Gr-800 exhibits a good performance in electrocatalytic activity, stability, and immunity towards methanol comparing with commercial carbon platinum(Pt/C) catalyst, the reduction potential and limiting current density of which were -0.137 V(vs. SCE) and 4.24 mA/cm², respectively. And the electron transfer number was 3.34.

Key words: Electrocatalyst, Oxygen reduction reaction, Carbon nanotubes, Graphene, Heteroatom doping

中图分类号:

O646

TrendMD:

狄沐昕, 肖国正, 黄鹏, 曹翊寰, 朱英. 钴/氮掺杂碳纳米管/石墨烯复合材料的构筑及氧还原催化性能. 高等学校化学学报, 2018, 39(2): 343.

DI Muxin, XIAO Guozheng, HUANG Peng, CAO Yihuan, ZHU Ying. Co/N Co-doped Carbon Nanotube/Graphene Composites as Efficient Electrocatalysts for Oxygen Reduction Reaction^†. Chem. J. Chinese Universities, 2018, 39(2): 343.

图/表 7

Fig.1 SEM images of Co-CNT/Gr(A), nanotubes in Co-CNT/Gr(B) and the corresponding C(C), Co(D) elemental mappings

Fig.2 TEM images of Co-CNT/Gr(A) and CNT in Co-CNT/Gr(B)

Fig.3 SEM images(A1—C1, A2—C2) and the corresponding C(A3—C3), Co(A4—C4) and N(A5—C5) elemental mappings of Co/N-CNT/Gr-800(A1—A5), Co/N-CNT/Gr-900(B1—B5) and Co/N-CNT/Gr-1000(C1—C5)

Fig.4 Raman spectra of Co-CNT/Gr(a), Co/N-CNT/Gr-800(b), Co/N-CNT/Gr-900(c) and Co/N-CNT/Gr-1000(d)

Fig.5 XPS spectra of Co-CNT/Gr(A1—A3) and Co/N-CNT/Gr-800(B1—B3) (A1), (B1) represent C1s spectra and the insets are the whole XPS spectra; (A2), (B2) and (A3), (B3) represent Co2p and N1s spectra, respectively.

Fig.6 CV curves of Pt/C(A), Co-CNT/Gr(B), Co/N-CNT/Gr-800(C), Co/N-CNT/Gr-900(D), Co/N-CNT/Gr-1000(E), LSV(F) and RRDE(G) curves of the Co-CNT/Gr, Co/N-CNT/Gr-X(X=800, 900, 1000) and Pt/C on GC electrodes(A)—(E) In O2-saturated(solid line) and N2-saturated(dashed line) 0.1 mol/L KOH at a scan rate of 50 mV/s; (F) in O2-saturated 0.1 mol/L KOH at a scan rate of 10 mV/s and a rotation rate of 1600 r/min; (G) in O2-saturated 0.1 mol/L KOH at a scan rate of 10 mV/s and a rotation rate of 1600 r/min.

Fig.7 Current-time curves of Co/N-CNT/Gr-800 and commercial Pt/C for electrodedurability(A) and tolerance to the methanol crossover(B) (A) in O2-saturated 0.1 mol/L KOH at -0.14 V and a rotation rate of 900 r/min; (B) in O2-saturated 0.1 mol/L KOH at -0.14 V and a rotation rate of 900 r/min. The arrow in (B) indicates the addition of 5 mL methanol into the electrochemical cell after about 100 s.

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