Abstract
Doped mesoporous carbons comprising nitrogen, boron, and phosphorus (N, B, and P, respectively) were prepared as non-Pt catalysts for oxygen reduction reaction (ORR) in an acidic solution. The N-doped carbons were varied to increase their catalytic activity through by additionally doping of B and P. All the mesoporous carbons were synthesized by carbonizing polyaniline at 900 °C for the N species, while the B and P species were inserted into the carbon structure at the carbon growth step. The linear sweep voltammogram recorded in the acidic solution showed that the ORR activity of the N-doped carbon catalysts increased significantly after the addition of B. An approximately 19 % increase in the pyridinic N content at the carbon surface was observed, along with B-N-C moieties with a binding energy of 399.5 eV. The non-precious metal ORR catalysts were prepared via pyrolysis, with the insertion of an additional transition metal (iron, Fe). The deconvoluted X-ray photoelectron spectroscopy (XPS) results showed that the Fe-N peak was generated after the pyrolysis. The peak intensity of the quaternary N also increased compared with the pyridic and pyrrolic N, which indicates that Fe serves to catalyze the modification of N species. The numerical examinations showed that N- and B-doped mesoporous carbon (NBC) 1.5 % Fe had the highest limited current (4.94 mA/cm2), with the B-doped carbon still the most active mesoporous carbon catalyst for ORR. As a result, it can be said that Fe positively contributes to the formation of graphitic N, which is known to be an active site for ORR. The cyclic voltammetry results showed that the peak area of the NBC 1.5 % Fe catalyst was larger than that of the N-doped mesoporous carbon (NC) 1.5 % Fe catalyst. It was concluded that B doping enhances the ORR activity and the stability of carbon materials even after 1000 cycles under acidic conditions.
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References
Nallathambi V, Lee JW, Kumaraguru SP, Wu G, Popov BN (2008) Development of high performance carbon composite catalyst for oxygen reduction reaction in PEM Proton Exchange Membrane fuel cells. J Power Sources 183:4–42
Feng Y, Vante NA (2008) Nonprecious metal catalysts for the molecular oxygen-reduction reaction. Phys Status Solidi B 245:1792–1806
Chen Z, Higgins D, Yu A, Zhang L, Zhang J (2011) A review on non-precious metal electrocatalysts for PEM fuel cells. Energy Environ Sci 4:3167–3192
Liu G, Li X, Ganesa 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 93:156–165
Yang DS, Bhattacharjya D, Inamar S, Park JS, Yu JS (2012) Phosphorus-doped ordered mesoporous carbons with different lengths as efficient metal-free electrocatalysts for oxygen reduction reaction in alkaline media. J Am Chem Soc 134:16127–16130
Liu ZW, Peng F, Wang HJ, Yu H, Zheng WX, Yang J (2011) Phosphorus-doped graphite layers with high electrocatalytic activity for the O2 reduction in an alkaline medium. Angew Chem Int Ed 50:3257–3261
Zhao X, Zhang Q, Zhang B, Chen CM, Wang A, Zhang T, Su DS (2012) Dual-heteroatom-modified ordered mesoporous carbon: Hydrothermal functionalization, structure, and its electrochemical performance. J Mater Chem 22:4963–4969
Li R, Wei Z, Gou X, Xu W (2013) Phosphorus-doped graphene nanosheets as efficient metal-free oxygen reduction electrocatalysts. R Soc Chem Adv 3:9978–9984
Ding S, Zheng S, Xie M, Peng L, Guo X, Ding W (2011) One-pot synthesis of boron-doped mesoporous carbon with boric acid as a multifunction reagent. Microporous Mesoporous Mater 142(2):609–613
Choi CH, Park SH, Woo SI (2012) Binary and ternary doping of nitrogen, boron, and phosphorus into carbon for enhancing electrochemical oxygen reduction activity. ACS Nano 6:7084–7091
Ozaki JI, Kimura N, Anahara T, Oya A (2007) Preparation and oxygen reduction activity of BN-doped carbons. Carbon 45:1847–1853
Yang L, Jiang S, Zhao Y, Zhu L, Chen S, Wang X, Wu Q, Ma J, Ma Y, Hu Z (2011) Boron-doped carbon nanotubes as metal-free electrocatalysts for the oxygen reduction reaction. Angew Chem Int Ed 50:7132–7135
Wu X, Radovic LR (2004) Ab initio molecular orbital study on the electronic structures and reactivity of boron-substituted carbon. J Phys Chem A 108:9180–9187
Radovic LR, Karra M, Skokova K, Thrower PA (1998) The role of substitutional boron in carbon oxidation. Carbon 36:1841–1854
Shiraishi S, Kibe M, Yokoyama T, Kurihara H, Patel N, Oya A, Kaburagi Y, Hishiyama Y (2006) Electric double layer capacitance of multi-walled carbon nanotubes and B-doping effect. Appl Phys A Mater Sci Process 82:585–591
Zhong DH, Sano H, Uchiyama Y, Kobayashi K (2000) Effect of low-level boron doping on oxidation behavior of polyimide-derived carbon films. Carbon 38:1199–1206
Wei D, Li F, Chen ZG, Lu GQ, Cheng HM (2008) Synthesis and electrochemical property of boron-doped mesoporous carbon in supercapacitor. Chem Mater 20:7195–7200
Jacques S, Guette A, Bourrat X, Langlais F, Gumon C, Labrugere C (1996) LPCVD and characterization of boron-containing pyrocarbon materials. Carbon 34:1135–1143
Zhai X, Song Y, Liu J, Li P, Zhong M, Ma C, Wang H, Guo Q, Zhi L (2012) In-situ preparation of boron-doped carbons with ordered mesopores and enhanced electrochemical properties in supercapacitors. J Electrochem Soc 159:177–182
Liu J, Liu H, Zhang Y, Li R, Liang G, Gauthier M, Sun X (2011) Synthesis and characterization of phosphorus–nitrogen doped multiwalled carbon nanotubes. Carbon 49:5014–5021
Silva EC, Urias FL, Sandoval EM, Sumpter BG, Terrones H, Chalier JC, Meunier V, Terrones M (2011) Phosphorus and phosphorus–nitrogen doped carbon nanotubes for ultrasensitive and selective molecular detection. Nanoscale 3:1008–1013
Choi CH, Park SH, Woo SI (2012) Phosphorus–nitrogen dual doped carbon as an effective catalyst for oxygen reduction reaction in acidic media: effects of the amount of P-doping on the physical and electrochemical properties of carbon. J Mater Chem 22:12107–12115
Davis CA, Yin Y, McKenzie DR, Hall LE, Kravtchinskaia E, Keast V, Amarantunga GAJ, Veerasamy VS (1994) The structure of boron-, phosphorus- and nitrogen-doped tetrahedral amorphous carbon deposited by cathodic arc. J Non-Cryst Solids 170:46–50
Kim SK, Cho HJ, Kim MY, Lee HJ, Park JH, Lee YB, Kim HC, Yoon CW, Nam SW, Kang SO (2013) Efficient catalytic conversion of ammonia borane to borazine and its use for hexagonal boron nitride (white graphene). J Mater Chem A 1:1976–1981
Panchakarla LS, Govindaraj A, Rao CNR (2010) Boron and nitrogen-doped carbon nanotubes and graphene. Inorg Chim Acta 363:4163–4174
Wang B, Ma YF, Wu Y, Li N, Huang Y, Chen Y (2009) Direct and large scale electric arc discharge synthesis of boron and nitrogen doped single-walled carbon nanotubes and their electronic properties. Carbon 47:2112–2142
Salazar PF, Kumar S, Cola BA (2012) Nitrogen- and boron-doped carbon nanotube electrodes in a thermo-electrochemical cell. J Electrochem Soc 159:483–488
Joseph G, Wiltshire LLJ, Herz LM, Nicholas RJ (2005) Chirality-dependent boron-mediated growth of nitrogen-doped single-walled carbon nanotubes. Phys Rev B 72:205431
Panchakarla LS, Govindaraj A, Rao CNR (2007) Nitrogen- and boron-doped double-walled carbon nanotubes. ACS Nano 1:491–500
Wang S, Iyyamperumal E, Roy A, Xue Y, Yu D, Dai L (2011) Vertically aligned BCN nanotubes as efficient metal-free electrocatalysts for the oxygen reduction reaction: a synergetic effect by Co-doping with boron and nitrogen. Angew Chem Int Ed 50:11756–11760
Maciel IO, Delgado JC, Pimenta MA, Terrones M, Terrones H, Rao AM, Jorio A (2009) Boron, nitrogen and phosphorous substitutionally doped single-wall carbon nanotubes studied by resonance Raman spectroscopy. Phys Status Solidi B 246:2432–2435
Koos AA, Dillon F, Obraztsova EA, Crossley A, Grobert N (2010) Comparison of structural changes in nitrogen and boron-doped multi-walled carbon nanotubes. Carbon 48:3033–3041
Jaclyn D, Wiggins C, Stevenson KJ (2009) Effect of nitrogen concentration on capacitance density of states electronic conductivity and morphology of N-doped carbon nanotube electrodes. J Phys Chem C 113:19082–19090
Rao CV, Ishikawa Y (2012) Activity selectivity and anion exchange membrane fuel cell performance of virtually metal-free nitrogen-doped carbon nanotube electrodes for oxygen reduction reaction. J Phys Chem C 116:4340–4346
Jaclyn D, Wiggins C, Stevenson KJ (2011) Mechanistic discussion of the oxygen reduction reaction at nitrogen-doped carbon nanotubes. J Phys Chem C 115:20002–20010
Rao CV, Cabrera CR, Ishikawa Y (2010) In search of the active site in nitrogen-doped carbon nanotube electrodes for oxygen reduction reaction. J Phys Chem Lett 1:2622–2627
Kim H, Lee K, Woo SI, Jung Y (2011) On the mechanism of enhanced oxygen reduction reaction in nitrogen-doped graphene nanoribbons. Phys Chem Chem Phys 13:17505–17510
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 17:2139–2149
Dorjgotov A, Ok JH, Jeon YW, 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 17:2567–2577
Can M, Akca B, Yilmaz A, Uner D (2002) Synthesis and characterization of Co-Pb/SBA-15 mesoporous catalysts. Turk J Phys 29:287–29
Zielke U, Huttinger KJ, Hoffman WP (1996) Surface-oxidized carbon fibers: I. Surface structure and chemistry. Carbon 34:983–998
Yeager E (1984) Electrocatalysts for O2 Reduction. Electrochim Acta 29:1527–1537
Wieser K (1986) N4-chelates as electrocatalyst for cathodic oxygen reduction. Electrochim Acta 31:1073–1078
Kundu S, Nagaiah TC, Xia W, Wang Y, Dommele SV, Bitter JH et al (2009) Electrocatalytic activity and stability of nitrogen-containing carbon nanotubes in the oxygen reduction reaction. J Phys Chem C 113:14302–14310
Okada T, Katou K, Hirose T, Yuasa M, Sekine I (1999) Oxygen reduction on pyrolytic graphite electrodes modified with electropolymerized cobalt salen compounds. J Electrochem Soc 146:2562–2568
Acknowledgments
This research was supported by the Technology innovation industrial Program funded by the Ministry of Trade, Industry and energy (MOTIE), Republic of Korea (No. 10052823) and by the New & Renewable Energy Core Technology Program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea (No. 20133030011320).
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Byambasuren, U., Jeon, Y., Altansukh, D. et al. Doping effect of boron and phosphorus on nitrogen-based mesoporous carbons as electrocatalysts for oxygen reduction reaction in acid media. J Solid State Electrochem 20, 645–655 (2016). https://doi.org/10.1007/s10008-015-3074-6
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DOI: https://doi.org/10.1007/s10008-015-3074-6