Iron-nitrogen-codoped Mesoporous Carbon: Facile Synthesis and Catalytic Performance of Oxygen Reduction Reaction

doi:10.15541/jim20230277

Abstract

Abstract:

Oxygen reduction reaction (ORR) is an important electrochemical reaction process at the cathode of fuel cell, but its spontaneous reaction process is slow, and its catalysts, though efficient in catalyzing the ORR reaction, are facing problems of expensive price, complicated synthesis process, and polluting environment. Therefore, it is of great significance to explore the method of synthesizing a simple and environmentally friendly catalyst for the preparation of ORR catalysts. Fe-N co-doped mesoporous carbon substrate (Fe-N/MC) is a kind of non-precious metal catalysts for oxygen reduction reaction with great application value. In this work, mesoporous carbon substrate (MC_M) was obtained by high-temperature carbonization of small molecule precursors in a semi-closed system in a muffle furnace, and then Fe-N co-doped mesoporous carbon substrate (Fe-N/MC_MT) was prepared by mixing the obtained MC_M with iron salts in a tube furnace at a high temperature. This method only needs simple pyrolysis conditions, requiring no template agents and toxic substances such as NH₃ and HF. MC_M is beneficial to enhance the hydrophilicity and coordination ability of the mesoporous carbon substrate surface due to its high element contents of nitrogen and oxygen. Fe-N/MC_MT, prepared by MC_M and iron salts, contains abundant and catalytic ORR Fe-N_x active sites with onset potential and half-wave potential of 0.941 and 0.831 V(vs RHE), respectively, which are 34 and 16 mV more positive than those of commercial Pt/C catalyst, respectively. ORR can be divided into two-electron or four-electron type according to the reaction process, and the transfer electron numbers of Fe-N/MCMT and Pt/C are 3.77 and 3.91, respectively, indicating a four-electron reaction process.

Key words: iron-nitrogen co-doped mesoporous carbon, oxygen reduction reaction, semi-containment system, catalyst

CLC Number:

TM911

YANG Daihui, SUN Tian, TIAN Hexin, SHI Xiaofei, MA Dongwei. Iron-nitrogen-codoped Mesoporous Carbon: Facile Synthesis and Catalytic Performance of Oxygen Reduction Reaction[J]. Journal of Inorganic Materials, 2023, 38(11): 1309-1315.

Figures/Tables 8

Fig. 1 Schematic diagram of Fe-N/MCMT catalyst synthesis

Fig. 2 (a) N2 adsorption-desorption isotherms, (b) pore-size distributions, (c) XRD patterns, and (d) Raman spectra of MCM, MCT, Fe-N/MCMT and Fe-N/MCTT

Fig. 3 HAADF-STEM images of (a-c) Fe-N/MCMT and (d-f) Fe-N/MCTT Single Fe atoms and Fe atom clusters are highlighted by white circles, respectively. Colorful figures are available on website

Fig. 4 High-resolution (a) N1s, (b) S2p and (c) Fe2p XPS spectra of MCM, MCT, Fe-N/MCMT, and Fe-N/MCTT

Fig. 5 ORR performance of catalysts (a) LSV curves of different catalysts in O2-saturated 0.1 mol/L KOH at a scan rate of 10 mV/s and a rotation rate of 1600 r/min; (b) LSV curves of Fe-N/MCMT at different rotation rates with inset showing K-L plots obtained from polarization curves; (c) Plots of number of electron transfer and H2O2 yield with different catalysts at the rotation speed of 1600 r/min; (d) Tafel plots derived from Fig. 6(a); (e, f) Chronoamperometric responses of Fe-N/MCMT and Pt/C in (e) presence or (f) absence of methanol at 0.7 V (vs RHE). Colorful figures are available on website

Table 1 Nitrogen content of each sample

Samples	N/%(in atomic)	Binding energy of relative nitrogen content/eV
Samples	N/%(in atomic)	Pyridinic N	Fe-N_x	Pyrollic N	Graphitic N	Oxygenated N
Fe-N/MC_MT	5.92	0.2 (398.2)	0.11 ( 399.3)		0.58 (401)	0.11 (403)
Fe-N/MC_TT	5.12	0.21 (398.1)	0.07 ( 399.2)		0.68 (401)	0.04 (403)
MC_M	16.48	0.41 (398.3)		0.39 (400)	0.16 (401)	0.04 (403)
MC_T	10.00	0.26 (398.3)		0.28 (400)	0.42 (400.98)	0.04 (403)

Table 2 Elemental percentages in atom of each sample

Sample	XPS
Sample	Fe/%	N/%	S/%	O/%	C/%
Fe-N/MC_MT	0.49	5.92	0.32	8.41	84.86
Fe-N/MC_TT	0.64	5.12	0.57	9.34	84.33
MC_M	0	16.48	1.27	7.92	74.33
MC_T	0	10	0.9	5	84.1

Fig. S1 Stability of MCM and MCT dispersed in water

References 24

[1]	JIANG L, XU S, XIA B, et al. Defect engineering of graphene hybrid catalysts for oxygen reduction reactions. J. Inorg. Mater., 2022, 37(2): 215. DOI
[2]	KIM D, ZUSSBLATT N P, CHUNG H T, et al. Highly graphitic mesoporous Fe, N-doped carbon materials for oxygen reduction electrochemical catalysts. ACS Appl. Mater. Interfaces, 2018, 10(30): 25337. DOI URL
[3]	SUN Y T, DING S, XU S S, et al. Metallic two-dimensional metal-organic framework arrays for ultrafast water splitting. J. Power Sources. 2021, 494: 229733. DOI URL
[4]	RAMASWAMY N, TYLUS U, JIA Q Y, et al. Activity descriptor identification for oxygen reduction on nonprecious electrocatalysts: linking surface science to coordination chemistry. J. Am. Chem. Soc., 2013, 135(41): 15443. DOI PMID
[5]	LEE S H, KIM J, CHUNG D Y, et al. Design principle of Fe-N-C electrocatalysts: how to optimize multimodal porous structures? J. Am. Chem. Soc., 2019, 141(5): 2035. DOI PMID
[6]	KONG A G, ZHU X F, HAN Z, et al. Ordered hierarchically micro- and mesoporous Fe-N_x-embedded graphitic architectures as efficient electrocatalysts for oxygen reduction reaction. ACS Catal., 2014, 4(6): 1793. DOI URL
[7]	NISHIHARA H, KYOTANI T. Templated nanocarbons for energy storage. Adv. Mater., 2012, 24(33): 4473. DOI URL
[8]	PENG Y, LU B Z, CHEN S W. Carbon-supported single atom catalysts for electrochemical energy conversion and storage. Adv. Mater., 2018, 30(48): 1801995. DOI URL
[9]	LEE J S, PARK G, KIM S T, et al. A highly efficient electrocatalyst for the oxygen reduction reaction: N-doped ketjenblack incorporated into Fe/Fe₃C-functionalized melamine foam. Angew. Chem. Int. Ed., 2013, 52(3): 1026. DOI URL
[10]	YANG L, CHENG D J, ZENG X F, et al. Unveiling the high- activity origin of single-atom iron catalysts for oxygen reduction reaction. Proc. Natl. Acad. Sci. U.S.A., 2018, 115(26): 6626. DOI URL
[11]	LU X, YIM W L, SURYANTO B H R, et al. Electrocatalytic oxygen evolution at surface-oxidized multiwall carbon nanotubes. J. Am. Chem. Soc., 2015, 137(8): 2901. DOI PMID
[12]	LIU J, JIAO M G, MEI B B, et al. Carbon-supported divacancy- anchored platinum single-atom electrocatalysts with superhigh Pt utilization for the oxygen reduction reaction. Angew. Chem. Int. Ed., 2019, 131(4): 1175. DOI URL
[13]	ZHANG S G, MANDAI T, UENO K, et al. Hydrogen-bonding spramolecular protic salt as an “all-in-one” precursor for nitrogen- doped mesoporous carbons for CO₂ adsorption. Nano Energy, 2015, 13: 376. DOI URL
[14]	XING C, YANG D H, ZHANG Y T, et al. Semi-closed synthesis of nitrogen and oxygen co-doped mesoporous carbon for selective aqueous oxidation. Green Energy Environ., 2022, 7(1): 43. DOI URL
[15]	SING K S. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl. Chem., 1985, 57(4): 603. DOI URL
[16]	DAS A, CHAKRABORTY B, SOOD A K B. Raman spectroscopy of graphene on different substrates and influence of defects. Mater. Sci., 2008, 31: 579.
[17]	WU Z Y, XU X X, HU B C, et al. Iron carbide nanoparticles encapsulated in mesoporous Fe-N-doped carbon nanofibers for efficient electrocatalysis. Angew. Chem. Int. Ed., 2015, 54(28): 8179. DOI URL
[18]	SUN M, DAVENPORT D, LIU H J, et al. Highly efficient and sustainable non-precious-metal Fe-N-C electrocatalysts for the oxygen reduction reaction. J. Mater. Chem. A, 2018, 6(6): 2527. DOI URL
[19]	SEROV A, ARTYUSHKOVA K, ATANASSOV P. Fe-N-C oxygen reduction fuel cell catalyst derived from carbendazim: synthesis, structure, and reactivity. Adv. Energy Mater., 2014, 4(10): 1301735. DOI URL
[20]	ZHAO Y X, LAI Q X, WANG Y, et al. Interconnected hierarchically porous Fe, N-codoped carbon nanofibers as efficient oxygen reduction catalysts for Zn-air batteries. ACS Appl. Mater. Interfaces, 2017, 9(19): 16178. DOI URL
[21]	DING Y J, NIU Y C, YANG J, et al. A metal-amino acid complex- derived bifunctional oxygen electrocatalyst for rechargeable zinc-air batteries. Small, 2016, 12(39): 5414. DOI URL
[22]	LEFEVRE M, PROIETTI E, JAOUEN F, et al. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science, 2009, 324(5923): 71. DOI PMID
[23]	LI J, SONG Y J, ZHANG G X, et al. Multicolor printing using electric-field-responsive and photocurable photonic crystals. Adv. Funct. Mater., 2017, 27(43): 1702825. DOI URL
[24]	CAO L, LI Z H, GU Y, et al. Rational design of n-doped carbon nanobox-supported Fe/Fe₂N/Fe₃C nanoparticles as efficient oxygen reduction catalysts for Zn-air batteries. J. Mater. Chem. A, 2017, 5(22): 11340. DOI URL