三维氮掺杂石墨烯气凝胶负载钴酞菁作为高效的氧气还原反应催化剂

doi:10.7503/cjcu20160607

摘要/Abstract

摘要：

通过两步溶剂热法制备得到三维氮掺杂石墨烯与吡啶氧基钴酞菁的复合材料(CoTPPc/NGA). 该复合材料具有优良的氧气还原性能, 在起峰电位和半波上接近商业化的铂碳催化剂(Pt/C), 且在稳定性和抗甲醇性能上优于铂碳催化剂, 有望代替铂碳催化剂成为碱性直接甲醇燃料电池的阴极催化剂.

关键词: 氮掺杂石墨烯, 气凝胶, 钴酞菁, 氧气还原反应

Abstract:

A two-step solvothermal approach for the synthesis of three-dimensional(3D) N-doped graphene aerogel and cobalt tetrapyridyloxyphthalocyanine composite(CoTPPc/NGA) as a novel and efficient non-precious catalyst in the oxygen reduction reaction(ORR) was reported. The resulted hybird exhibited impressive ORR catalytic activity and superior stability as well as excellent methanol crossover to commercial Pt/C, which could be used as an alternative Pt-free catalyst in alkaline direct methanol fuel cells(DMFCs).

Key words: N-Doped graphene, Aerogel, Cobalt phthalocyanine, Oxygen reduction reaction

中图分类号:

O646
TM911.4

TrendMD:

俞丁凌, 张博文, 何兴权. 三维氮掺杂石墨烯气凝胶负载钴酞菁作为高效的氧气还原反应催化剂. 高等学校化学学报, 2016, 37(12): 2176.

YU Dingling, ZHANG Bowen, HE Xingquan. Three-dimensional N-Doped Graphene Aerogel Supported Cobalt Phthalocyanine as High-efficiency Catalyst for Oxygen Reduction Reaction^†. Chem. J. Chinese Universities, 2016, 37(12): 2176.

图/表 10

Scheme 1 Synthetic routes of CoTPPc

Scheme 2 Synthetic procedures of CoTPPc/NGA compositesa. Stable suspension of GO, 2,5-diaminopyridine and urea dispersed in a avial; b. the bulk aerogel of NGA obtained after a free-drying process; c. the CoTPPc/NGA hybrid fabricated by a solvothermal method with different mass ratios.

Fig.1 SEM(A, B) and TEM(C, D) images of NGA(A, C) and CoTPPc/NGA(B, D)

Fig.2 UV-Vis absorption spectra of CoTPPc(a), CoTPPc/NGA(b) and NGA(c)(A) and FTIR spectra of CoTPPc(a) and CoTPPc/NGA(b)(B)

Fig.3 XPS spectra of NGA(a), CoTPPc(b) and CoTPPc/NGA(c)(A), high-resolution Co2p XPS spectra of CoTPPc(a) and CoTPPc/NGA(b)(B), N1s XPS spectra of CoTPPc(C) and CoTPPc/NGA(D) and N2 adsorption(a)-desorption(b) isotherms of NGA(E) and CoTPPc/NGA(F)Insets in (E) and (F) are the corresponding pore size distribution curves.

Fig.4 CV curves of CoTPPc/NGA composite with different mass ratios in a 0.1 mol/L KOH solution saturated by O2 or N2 atmosphere(A) and CV curves of different samples in an O2-saturated 0.1 mol/L KOH solution(B)(B) Catalyst loading is 282 μg/cm2.

Fig.5 LSV curves of CoTPPc/NGA(A) and Pt/C(C) at different rotation rates in an O2-saturated 0.1 mol/L KOH solution with a scan rate of 10 mV/s, K-L plots of CoTPPc/NGA(B) and Pt/C(D) at fixed potentials of 0.69, 0.59, 0.49, 0.39 and 0.29 V(vs. RHE), electron transfer number at different potentials for NGA, CoTPPc, CoTPPc/NGA and Pt/C(E) and LSV curves of different samples at 1600 r/min in an O2-saturated 0.1 mol/L KOH solution with a scan rate of 10 mV/s(F)Catalyst loading: 282 μg/cm2.

Table 1 Electrochemical parameters for oxygen reduction reaction(ORR) estimated from LSVs

Material	Limiting current density/(mA·cm^-2)	Onset potential/V(vs. RHE)	Half wave potential/V(vs. RHE)
NGA	3.611	0.894	0.787
CoTPPc	2.842	0.862	0.741
CoTPPc/NGA	6.056	0.933	0.816
Pt/C	5.766	0.965	0.829

Fig.6 RRDE tests of ORR on NGA, CoTPPc, CoTPPc/NGA and Pt/C in an O2-saturated 0.1 mol/L KOH solution at a rotation rate of 1600 r/min and at the scan rate of 10 mV/s, electron transfer number(B) and peroxide percentage of NGA, CoTPPc, CoTPPc/NGA and Pt/C(C) at different potentialsThe ring electrode is polarized at 1.29 V vs. RHE; the catalyst loading is 282 μg/cm2.

Fig.7 Current density-time chronoamperometric responses of Pt/C and CoTPPc/NGA electrodes at 0.8 V(vs. RHE) at a rotation rate of 1600 r/min in an oxygen-saturated 0.1 mol/L KOH solution(A) and the durability of CoTPPc/NGA(a) and Pt/C(b) for ORR(B)The arrow indicates the addition of methanol into the electrolytic cell.

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