Abstract
Two iron precursors (iron(III) chloride and iron(II) ammonium sulfate) with a nitrogen-containing compound (ethylenediamine) were pyrolyzed on commercially available carbon blacks (Vulcan XC-72) under a nitrogen flow in this study. The properties of the resultant nonnoble electrocatalysts (Fe(Z)N/C-2 and Fe(Z)N/C-8) effected by using different iron precursors during the synthetic process were investigated by X-ray-based spectroscopies including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS). The electrocatalytic performance toward oxygen reduction reaction (ORR) of these electrocatalysts was also comparatively studied by rotating disk electrode and chronoamperometric techniques. The obtained results indicate that iron precursors play an essential role on the chemical microstructure, elemental states, and ORR performance of electrocatalysts. The electrocatalysts (Fe(III)N/C-8) prepared by using iron(III) chloride as starting precursors exhibit better electrochemical ORR activity and durability among all the synthesized catalysts. As evidenced by XPS and XAS studies, we conclude that this may be due to the formation of active FeN x sites, more surface Fe/C and N/C atomic ratios, and the coexistence of pyridinic-N and graphitic-N species in the Fe(III)N/C-8 electrocatalyst.
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.References
Guterman VE, Lastovina TA, Belenov SV, Tabachkova NY, Vlasenko VG, Khodos II, Balakshina EN (2014) PtM/C (M = Ni, Cu, or Ag) electrocatalysts: effects of alloying components on morphology and electrochemically active surface areas. J Solid State Electrochem 18(5):1307–1317
Liu S-H, Chen S-C, Sie W-H (2011) Heat-treated platinum nanoparticles embedded in nitrogen-doped ordered mesoporous carbons: synthesis, characterization and their electrocatalytic properties toward methanol-tolerant oxygen reduction. Int J Hydrogen Energy 36:15060–15067
Sepp S, Haerk E, Valk P, Vaarmets K, Nerut J, Jaeger R, Lust E (2014) Impact of the Pt catalyst on the oxygen electroreduction reaction kinetics on various carbon supports. J Solid State Electrochem 18(5):1223–1229
Brouzgou A, Song SQ, Tsiakaras P (2012) Low and non-platinum electrocatalysts for PEMFCs: current status, challenges and prospects. Appl Catal B Environ 127:371–388
Soin N, Roy SS, Sharma S, Thundat T, McLaughlin JA (2013) Electrochemical and oxygen reduction properties of pristine and nitrogen-doped few layered graphene nanoflakes (FLGs). J Solid State Electrochem 17(8):2139–2149
Liu S-H, Zheng F-S, Wu J-R (2011) Preparation of ordered mesoporous carbons containing well-dispersed and highly alloying Pt-Co bimetallic nanoparticles toward methanol-resistant oxygen reduction reaction. Appl Catal B Environ 108:81–89
Yin W, Chen CG, Fa HB, Zhang LP (2013) Electropolymerization of CoTPP and its catalytic performance for oxygen-reduction reaction in an acid medium. J Solid State Electrochem 17(12):3095–3099
Ziegelbauer JM, Gatewood D, Gulla AF, Guinel MJF, Ernst F, Ramaker DE, Mukerjee S (2009) Fundamental investigation of oxygen reduction reaction on rhodium sulfide-based chalcogenides. J Phys Chem C 113:6955–6968
Dorjgotov A, Ok J, Jeon Y, Yoon SH, Shul YG (2013) Nitrogen-doped ordered porous carbon catalyst for oxygen reduction reaction in proton exchange membrane fuel cells. J Solid State Electrochem 17(10):2567–2577
Ganesan S, Leonard N, Barton SC (2014) Impact of transition metal on nitrogen retention and activity of iron-nitrogen-carbon oxygen reduction catalysts. Phys Chem Chem Phys 16(10):4576–4585
Bezerra CWB, Zhang L, Lee K, Liu H, Marques ALB, Marques EP, Wang HJ, Zhang JJ (2008) A review of Fe-N/C and Co-N/C catalysts for the oxygen reduction reaction. Electrochim Acta 53:4937–4951
Liu G, Li X, Ganesan P, Popov BN (2009) Development of non-precious metal oxygen-reduction catalysts for PEM fuel cells based on N-doped ordered porous carbon. Appl Catal B Environ 93:156–165
Zhang L, Lee K, Bezerra CWB, Zhang JL, Zhang JJ (2009) Fe loading of a carbon-supported Fe-N electrocatalyst and its effect on the oxygen reduction reaction. Electrochim Acta 54:6631–6636
Charreteur F, Jaouen F, Dodelet JP (2009) Iron porphyrin-based cathode catalysts for PEM fuel cells: influence of pyrolysis gas on activity and stability. Electrochim Acta 54:6622–6630
Choi JY, Hsu RS, Chen ZW (2010) Highly active porous carbon-supported nonprecious metal-N electrocatalyst for oxygen reduction reaction in PEM fuel cells. J Phys Chem C 114:8048–8053
Palaniselvam T, Aiyappa HB, Kurungot S (2012) An efficient oxygen reduction electrocatalyst from graphene by simultaneously generating pores and nitrogen doped active site. J Mater Chem 22:23799–23805
Brocato S, Serov A, Atanassov P (2013) pH dependence of catalytic activity for ORR of the non-PGM catalyst derived from heat-treated Fe-phenanthroline. Electrochim Acta 87:361–365
Liu Y, Wu YY, Lv GL, Pu T, He XQ, Cui LL (2013) Iron(II) phthalocyanine covalently functionalized graphene as a highly efficient non-precious-metal catalyst for the oxygen reduction reaction in alkaline media. Electrochim Acta 112:269–278
Yuan XX, Hu XX, Ding XL, Kong HC, Sha HD, Lin H, Wen W, Shen GX, Guo Z, Ma Z, Yang Y (2013) Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction. Nanoscale Res Lett 8:478
Liu S-H, Wu J-R, Pan C-J, Hwang B-J (2014) Synthesis and characterization of carbon incorporated Fe-N/carbons for methanol-tolerant oxygen reduction reaction of polymer electrolyte fuel cells. J Power Sources 250:279–285
Lima FHB, de Castro JFR, Santos LGRA, Ticianelli EA (2009) Electrocatalysis of oxygen reduction on carbon-supported Pt-Co nanoparticles with low Pt content. J Power Sources 190:293–300
Malheiro AR, Perez J, Villullas HM (2010) Surface structure and electronic properties of Pt-Fe/C nanocatalysts and their relation with catalytic activity for oxygen reduction. J Power Sources 195:3111–3118
Hwang SJ, Yoo SJ, Jang S, Lim TH, Hong SA, Kim SK (2011) Ternary Pt-Fe-Co alloy electrocatalysts prepared by electrodeposition: elucidating the roles of Fe and Co in the oxygen reduction reaction. J Phys Chem C 115:2483–2488
Loukrakpam R, Luo J, He T, Chen YS, Xu ZC, Njoki PN, Wanjala BN, Fang B, Mott D, Yin J, Klar J, Powell B, Zhong CJ (2011) Nanoengineered PtCo and PtNi catalysts for oxygen reduction reaction: an assessment of the structural and electrocatalytic properties. J Phys Chem C 115:1682–1694
Ishiguro N, Saida T, Uruga T, Nagamatsu S, Sekizawa O, Nitta K, Yamamoto T, Ohkoshi S, Iwasawa Y, Yokoyama T, Tada M (2012) Operando time-resolved X-ray absorption fine structure study for surface events on a Pt3Co/C cathode catalyst in a polymer electrolyte fuel cell during voltage-operating processes. ACS Catal 2:1319–1330
Liu S-H, Yu W-Y, Chen C-H, Lo A-Y, Hwang B-J, Chien S-H, Liu S-B (2008) Fabrication and characterization of well-dispersed and highly stable PtRu nanoparticles on carbon mesoporous material for applications in direct methanol fuel cell. Chem Mater 20:1622–1628
Goto S, Hosoi S, Arai R, Tanaka S, Umeda M, Yoshimoto M, Kudo Y (2014) Particle-size- and Ru-core-induced surface electronic states of Ru-core/Pt-shell electrocatalyst nanoparticles. J Phys Chem C 118:2634–2640
Ravel B, Newville M (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J Synchrotron Radiat 12:537–541
Pels JR, Kapteijn F, Moulijn JA, Zhu Q, Thomas KM (1995) Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis. Carbon 33:1641–1653
Oh HS, Kim H (2012) The role of transition metals in non-precious nitrogen-modified carbon-based electrocatalysts for oxygen reduction reaction. J Power Sources 212:220–225
Liu G, Li XG, Lee JW, Popov BN (2011) A review of the development of nitrogen-modified carbon-based catalysts for oxygen reduction at USC. Catal Sci Technol 1:207–217
Kim H, Lee K, Woo SI, Jung YS (2011) On the mechanism of enhanced oxygen reduction reaction in nitrogen-doped graphene nanoribbons. Phys Chem Chem Phys 13:17505–17510
Zhang J, He DP, Su H, Chen X, Pan M, Mu SC (2014) Porous polyaniline-derived FeNxC/C catalysts with high activity and stability towards oxygen reduction reaction using ferric chloride both as an oxidant and iron source. J Mater Chem A 2:1242–1246
Sevilla M, Yu LH, Fellinger TP, Fuertes AB, Titirici M (2013) Polypyrrole-derived mesoporous nitrogen-doped carbons with intrinsic catalytic activity in the oxygen reduction reaction. RSC Adv 3:9904–9910
Luo Z, Lim S, Tian Z, Shang J, Lai L, MacDonald B, Fu C, Shen ZX, Yu T, Lin JY (2011) Pyridinic N doped graphene: synthesis, electronic structure, and electrocatalytic property. J Mater Chem 21:8038–8044
Unni SM, Devulapally S, Karjule N, Kurungot S (2012) Graphene enriched with pyrrolic coordination of the doped nitrogen as an efficient metal-free electrocatalyst for oxygen reduction. J Mater Chem 22(44):23506–23513
Choudhury T, Saied SO, Sullivan JL, Abbot AM (1989) Reduction of oxides of iron, cobalt, titanium and niobium by low-energy ion bombardment. J Phys D Appl Phys 22:1185–1195
Biwer BM, Bernasek SL (1986) Electron spectroscopic study of the iron surface and its interaction with oxygen and nitrogen. J Electron Spectrosc Relat Phenom 40:339–351
Iwasawa Y (1996) X-ray absorption fine structure for catalyst and surfaces. World Scientific, Singapore
Liu S-H, Wu M-T, Lai Y-H, Chiang C-C, Yu N, Liu S-B (2011) Fabrication and electrocatalytic performance of highly stable and active platinum nanoparticles supported on nitrogen-doped ordered mesoporous carbons for oxygen reduction reaction. J Chem Mater 21:12489–12496
Xiao H, Shao ZG, Zhang G, Gao Y, Lu WT, Yi BL (2013) Fe-N-carbon black for the oxygen reduction reaction in sulfuric acid. Carbon 57:443–451
Liu S-H, Wu J-R (2011) Nitrogen-doped ordered mesoporous carbons as electrocatalysts for methanol-tolerant oxygen reduction in acid solution. Int J Hydrogen Energy 36:87–93
Wu HM, Wexler D, Liu HK (2011) Durability investigation of graphene-supported Pt nanocatalysts for PEM fuel cells. J Solid State Electrochem 15(5):1057–1062
Selvaganesh SV, Sridhar P, Pitchumani S, Shukla AK (2014) Pristine and graphitized-MWCNTs as durable cathode-catalyst supports for PEFCs. J Solid State Electrochem 18(5):1291–1305
Acknowledgments
Financial support of this work from the Ministry of Science and Technology of Taiwan (Contract No. NSC99-2221-E-151-044-MY2) is gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Liu, SH., Wu, JR., Zheng, FS. et al. Impact of iron precursors on the properties and activities of carbon-supported Fe-N oxygen reduction catalysts. J Solid State Electrochem 19, 1381–1391 (2015). https://doi.org/10.1007/s10008-015-2759-1
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10008-015-2759-1