Preparation and Oxygen Reduction Performance of Fe, N co-Doped arbon Nanoplate with High Density of Active Sites†

doi:10.7503/cjcu20190020

Abstract

Abstract:

Fe, N co-doped carbon nanoplate catalyst with high active sites was developed via methods of polymerization of triazine polyimide and carbonization within melting salt of ZnCl₂/KCl with the aid of g-C₃N₄ to anchor Fe³⁺. The as-prepared NPT-C₃N₄-0.5 catalyst displays high specific surface area of 1794 m²/g. The iron atoms uniformly distribute in the carbon skeleton with an increased doping amount up to the molar percentage of 1.13%, 3.3 times of the one without g-C₃N₄, which can be attributed to the coordination between g-C₃N₄ and iron to decrease its aggregation under high temperature. The catalyst exhibits excellent catalytic activity for oxygen reduction reaction(ORR) in acid media. Typically, the half-wave potential(E_1/2) of the catalyst can reach up to 0.79 V(vs. RHE) and only decreases by 30 mV after 10000 potential cycles of accelerated durability test in acid media, showing high activity towards ORR.

Key words: Non-precious metal catalyst, Oxygen reduction reaction, Graphitic carbon nitride, Coordination, Polyimide

CLC Number:

O646

TrendMD:

YIN Wenjing, LIU Xiao, QIAN Huidong, ZOU Zhiqing. Preparation and Oxygen Reduction Performance of Fe, N co-Doped arbon Nanoplate with High Density of Active Sites^†[J]. Chem. J. Chinese Universities, 2019, 40(7): 1480.

Figures/Tables 9

Scheme 1 Schematic illustration of the synthesis of polyimide with triazine structure(Ⅰ) and NPT-C3N4 catalysts(Ⅱ)

Fig.1 FTIR spectra of melamine(a), PMDA(b) and polyimide(c)(A), assembly illustration of g-C3N4 and FeCl3(B), zeta potential of g-C3N4(C) and FTIR spectra of g-C3N4(a) and g-C3N4-FeCl3(b)(D)

Fig.2 TEM images of NPT-C3N4-0.5

Fig.3 TEM image(A) and elemental EDS-mapping analysis of C(B), N(C), O(D) and Fe(E) in the NPT-C3N4-0.5 nanoplate

Fig.4 XRD patterns(A), N2 adsorption-desorption isotherms(B) and pore size distribution(C) of NPT-C3N4-N(N=0, 0.2, 0.5, 1.0) catalysts

Fig.5 Survey XPS spectra(A) and high-resolution deconvoluted N1s XPS spectra of NPT-C3N4-0(B), NPT-C3N4-0.2(C), NPT-C3N4-0.5(D) and NPT-C3N4-1.0(E) N1: Pyridinic N; N2: pyrrolic N; N3: graphitic N; N4: oxidized N.

Table 1 XPS analysis of NPT-C3N4-N(N=0, 0.2, 0.5, 1.0) catalysts

Sample	Atomic fraction(%)		Percentage of different N(%)
Sample	Fe	N	Pyridinic N	Graphitic N	Pyrrolic N	Oxidized N
NPT-C₃N₄-0	0.43	6.53	24.8	43.1	7.2	24.9
NPT-C₃N₄-0.2	0.68	6.05	24.2	37.5	13.7	24.6
NPT-C₃N₄-0.5	1.13	5.57	31.0	32.1	13.1	23.7
NPT-C₃N₄-1.0	0.95	4.85	22.4	31.5	16.1	30.0

Fig.6 ORR polarization curves of NPT-C3N4-N(N=0, 0.2, 0.5, 1.0) catalysts and commercial Pt/C(20%) catalysts in 0.1 mol/L HClO4 solution at rotating rate of 1600 r/min with a scan rate of 10 mV/s(A) and H2O2 yield and average electron transfer number of NPT-C3N4-0.5(B)

Fig.7 ORR polarization curves of NPT-C3N4-0.5 and Pt/C before and after 10000 cycles accelerated durability test(0.6—1.0 V, 50 mV/s)(A) and methanol tolerance test of NPT-C3N4-0.5 and Pt/C(B)Rotational speed: 1600 r/min; catalyst loadings: 0.6 mg/cm2 for NPT-C3N4-N(N=0, 0.2, 0.5, 1.0), 0.1 mg/cm2 for Pt/C.

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