Fe/N-doped mesoporous carbons derived from soybeans: A highly efficient and low-cost non-precious metal catalyst for ORR

Abstract

Oxygen reduction reaction (ORR) plays a crucial role in many energy storage and conversion devices. Currently, the development of inexpensive and high-performance carbon-based non-precious-metal ORR catalysts in alkaline media still gains a wide attention. In this paper, the mesoporous Fe-N/C catalysts were synthesized through SiO₂-mediated templating method using biomass soybeans as the nitrogen and carbon sources. The SiO₂ templates create a simultaneous optimization of both the surface functionalities and porous structures of Fe-N/C catalysts. Detailed investigations indicate that the Fe-N/C3 catalyst prepared with the mass ratio of SiO₂ to soybean being 3:4 exhibits brilliant electrocatalytic performance, excellent long-term stability and methanol tolerance for the ORR, with the onset potential and the half-wave potential of the ORR being about 0.890 V and 0.783 V (vs RHE), respectively. Meanwhile, the desired 4-electron transfer pathway of the ORR on the catalysts can be observed. It is significantly proposed that the high BET specific surface area and the appropriate pore-size, as well as the high pyridinic-N and total nitrogen loadings may play key roles in enhancing the ORR performance for the Fe-N/C3 catalyst. These results suggest a feasible route based on the economical and sustainable soybean biomass to develop inexpensive and highly efficient non-precious metal electrochemical catalysts for the ORR.

Keywords

biomass / oxygen reduction reaction / electro-catalyst / nitrogen-doped carbon

References

[1] KakatiN, MaitiJ, LeeS H, JeeS H, ViswanathanB, YoonY S. Anode catalysts for direct methanol fuel cells in acidic media: Do we have any alternative for Pt or Pt-Ru? [J]. Chemical Reviews, 2014, 114(24): 12397-12429

[2] XuY, ZhangBin. Recent advances in porous Pt-based nanostructures: synthesis and electrochemical applications [J]. Chemical Society Reviews, 2014, 43(8): 2439-2450

[3] BashyamR, ZelenayPA class of non-precious metal composite catalysts for fuel cells [C]// Materials for Sustainable Energy: A Collection of Peer-Reviewed Research and Review Articles from Nature Publishing Group, 2011247250

[4] LefevreM, ProiettiE, JaouenF, DodeletJ P. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells [J]. Science, 2009, 324(5923): 71-74

[5] TanH-b, LiY-q, JiangX-f, TangJ, WangZ-l, QianH-y, MeiP, MalgrasV, BandoY, YamauchiY. Perfectly ordered mesoporous iron-nitrogen doped carbon as highly efficient catalyst for oxygen reduction reaction in both alkaline and acidic electrolytes [J]. Nano Energy, 2017, 36: 286-294

[6] ZhangL-j, SuZ-x, JiangF-l, YangL-l, QianJ-j, ZhouY-f, LiW-m, HongM-chun. Highly graphitized nitrogen-doped porous carbon nanopolyhedra derived from ZIF-8 nanocrystals as efficient electrocatalysts for oxygen reduction reactions [J]. Nanoscale, 2014, 6(12): 6590-6602

[7] BiswalB P, ChandraS, KandambethS, LukoseB, HeineT, BanerjeeR. Mechanochemical synthesis of chemically stable isoreticular covalent organic frameworks [J]. Journal of the American Chemical Society, 2013, 135(14): 5328-5331

[8] WangK-l, WangH, JiS, FengH-q, LinkovV, WangR-fang. Biomass-derived activated carbon as high-performance non-precious electrocatalyst for oxygen reduction [J]. Rsc Advances, 2013, 3(30): 12039-12042

[9] GuoC-z, LiaoW-l, LiZ-b, SunL-t, ChenC-guo. Easy conversion of protein-rich enoki mushroom biomass to a nitrogen-doped carbon nanomaterial as a promising metal-free catalyst for oxygen reduction reaction [J]. Nanoscale, 2015, 7(38): 15990-15998

[10] LiuY-y, RuanJ-m, SangS-b, ZhouZ-c, WuQ-mei. Iron and nitrogen co-doped carbon derived from soybeans as efficient electro-catalysts for the oxygen reduction reaction [J]. Electrochimica Acta, 2016, 215: 388-397

[11] LiangJ, ZhengY, ChenJ, LiuJ, Hulicova-JurcakovaD, JaroniecM, QiaoS-zhang. Facile oxygen reduction on a three-dimensionally ordered macroporous graphitic C3N4/carbon composite electrocatalyst [J]. Angewandte Chemie: International Edition, 2012, 51(16): 3892-3896

[12] SunZ-k, LiuY, LiB, WeiJ, WangM-h, YueQ, DengY-h, KaliaguineS, ZhaoD-yuan. General synthesis of discrete mesoporous carbon microspheres through a confined self-assembly process in inverse opals [J]. Acs Nano, 2013, 7(10): 8706-8714

[13] LeeJ, KimJ, HyeonT. Recent progress in the synthesis of porous carbon materials [J]. Advanced Materials, 2006, 18(16): 2073-2094

[14] WangZ-l, ZhangX-b, LiuX-j, LvM-f, YangK-y, MengJian. Co-gelation synthesis of porous graphitic carbons with high surface area and their applications [J]. Carbon, 2011, 49(1): 161-169

[15] PengH-l, HouS-y, DangD, ZhangB-q, LiuF-f, ZhengR-p, LuoF, SongH-y, HuangP-y, LiaoS-jun. Ultra-high-performance doped carbon catalyst derived from o-phenylenediamine and the probable roles of Fe and melamine [J]. Applied Catalysis B: Environmental, 2014158159

[16] MaZ-l, HuangX-b, DouS, WuJ-h, WangS-yin. One-Pot synthesis of Fe₂O₃ nanoparticles on nitrogen-doped graphene as advanced supercapacitor electrode materials [J]. Journal of Physical Chemistry C, 2014, 118(31): 17231-17239

[17] SunM, DongY-z, ZhangG, QuJ-h, LiJ-hong. Alpha-Fe₂O₃ spherical nanocrystals supported on CNTs as efficient non-noble electrocatalysts for the oxygen reduction reaction [J]. Journal of Materials Chemistry A, 2014, 2(33): 13635-13640

[18] HanZ, TangZ-h, LiP, YangG-z, ZhengQ-b, YangJunhe. Ammonia solution strengthened three-dimensional macro-porous graphene aerogel [J]. Nanoscale, 2013, 5(12): 5462-5467

[19] LinZ-y, SongM-k, DingY, LiuY, LiuM, WongC-ping. Facile preparation of nitrogen-doped graphene as a metal-free catalyst for oxygen reduction reaction [J]. Physical Chemistry Chemical Physics, 2012, 14(10): 3381-3387

[20] LiX-l, WangH-l, RobinsonJ T, SanchezH, DiankovG, DaiH-jie. Simultaneous nitrogen doping and reduction of graphene oxide [J]. Journal of the American Chemical Society, 2009, 131(43): 15939-15944

[21] ChoushuryD, DasB, SarmaD D, RaoC N R. Xps evidence for molecular charge-transfer doping of graphene [J]. Chemical Physics Letters, 2010, 497(1): 66-69

[22] GuoD-h, ShibuyaR, AkibaC, SajiS, KondoT, NakamuraJ. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts [J]. Science, 2016, 351(6271): 361-365

[23] YuD-s, ZhangQ, DaiL-ming. Highly efficient metal-free growth of nitrogen-doped single-walled carbon nanotubes on plasma-etched substrates for oxygen reduction [J]. Journal of the American Chemical Society, 2010, 132(43): 15127-15129

[24] YamashitaT, HayesP. Analysis of Xpps spectra of Fe²⁺, and Fe³⁺, ions in oxide materials [J]. Applied Surface Science, 2008, 254(8): 2441-2449

[25] MillsP, SullivanJ L. A study of the core level electrons in iron and its three oxides by means of X-ray photoelectron spectroscopy [J]. Journal of Physics D: Applied Physics, 2000, 16(5): 723

[26] MouF-z, GuanJ-g, XiaoZ-d, SunZ-g, ShiW-d, FanX-an. Solvent-mediated synthesis of magnetic Fe₂O₃ chestnut-like amorphous-core/γ-phase-shell hierarchical nanostructures with strong As(V) removal capability [J]. Journal of Materials Chemistry, 2011, 21145414-5421

[27] KawabeT, ShimomuraS, KarasudaT, TabataK, SuzukiE, YamaguchiY. Photoemission study of dissociatively adsorbed methane on a pre-oxidized SnO2, thin film [J]. Surface Science, 2000, 448(2): 101-107

[28] KrukM, JaroniecM. Gas adsorption characterization of ordered organic-inorganic nanocomposite materials [J]. Chemistry of Materials, 2001, 13(10): 3169-3183

[29] ChmiolaJ, YushinG, GogotsiY, PortetC, SimonP, TabernaP L. Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer [J]. Science, 2006, 313(5794): 1760-1763

[30] PanF-p, CaoZ-y, ZhaoQ-p, LiangH-y, ZhangJ-yan. Nitrogen-doped porous carbon nanosheets made from biomass as highly active electrocatalyst for oxygen reduction reaction [J]. Journal of Power Sources, 2014, 272: 8-15

[31] GouC-z, LiaoW-l, ChenC-guo. Design of a non-precious metal electrocatalyst for alkaline electrolyte oxygen reduction by using soybean biomass as the nitrogen source of electrocatalytically active center structures [J]. Journal of Power Sources, 2014, 269(4): 841-847

[32] TongF, LiaoW-l, LiZ-b, SunL-t, ShiD-p, GuoC-z, HuangY, WangY, ChengJ, LiY-r, DiaoQ-zhi. Heavily graphitic-nitrogen self-doped high-porosity carbon for the electrocatalysis of oxygen reduction reaction [J]. Nanoscale Research Letters, 2017, 12(1): 595

[33] PanS-y, CaiZ, DuanY-q, YangL, TangB, JingB-j, DaiY, XuX, ZouJ-long. Tungsten diselenide/porous carbon with sufficient active edge-sites as a co-catalyst/Pt-support favoring excellent tolerance to methanol-crossover for oxygen reduction reaction in acidic medium [J]. Applied Catalysis B: Environmental, 2017, 21918-29