Three-dimensional N-Doped Graphene Aerogel Supported Cobalt Phthalocyanine as High-efficiency Catalyst for Oxygen Reduction Reaction†

doi:10.7503/cjcu20160607

Abstract

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

CLC Number:

O646
TM911.4

TrendMD:

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

Figures/Tables 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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