High activity and durability of carbon-supported core-shell PtPx@Pt/C catalyst for oxygen reduction reaction

doi:10.1016/S1872-2067(21)63901-3

Abstract

Abstract:

Alloying Pt with transition metals can significantly improve the catalytic properties for the oxygen reduction reaction (ORR). However, the application of Pt-transition metal alloys in fuel cells is largely limited by poor long-term durability because transition metals can easily leach. In this study, we developed a nonmetallic doping approach and prepared a P-doped Pt catalyst with excellent durability for the ORR. Carbon-supported core-shell nanoparticles with a P-doped Pt core and Pt shell (denoted as PtP_x@Pt/C) were synthesized via heat-treatment phosphorization of commercial Pt/C, followed by acid etching. Compositional analysis using electron energy loss spectroscopy and X-ray photoelectron spectroscopy clearly demonstrated that Pt was enriched in the near-surface region (approximately 1 nm) of the carbon-supported core-shell nanoparticles. Owning to P doping, the ORR specific activity and mass activity of the PtP_1.4@Pt/C catalyst were as high as 0.62 mA cm^-2 and 0.31 mA μg_Pt^-1, respectively, at 0.90 V, and they were enhanced by 2.8 and 2.1 times, respectively, in comparison with the Pt/C catalyst. More importantly, PtP_1.4@Pt/C exhibited superior stability with negligible mass activity loss (6% after 30000 potential cycles and 25% after 90000 potential cycles), while Pt/C lost 46% mass activity after 30000 potential cycles. The high ORR activity and durability were mainly attributed to the core-shell nanostructure, the electronic structure effect, and the resistance of Pt nanoparticles against aggregation, which originated from the enhanced ability of the PtP_1.4@Pt to anchor to the carbon support. This study provides a new approach for constructing nonmetal-doped Pt-based catalysts with excellent activity and durability for the ORR.

Key words: Oxygen reduction reaction, Nonmetallic doping, Phosphorization, Core-shell nanostructure, Durability

Wei-Ze Li, Bang-An Lu, Lin Gan, Na Tian, Peng-Yang Zhang, Wei Yan, Wei-Xin Chen, You-Hu Chen, Zhi-You Zhou, Shi-Gang Sun. High activity and durability of carbon-supported core-shell PtP_x@Pt/C catalyst for oxygen reduction reaction[J]. Chinese Journal of Catalysis, 2021, 42(12): 2173-2180.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63901-3

https://www.cjcatal.com/EN/Y2021/V42/I12/2173

Figures/Tables 6

Fig. 1. TEM image (a) and particle size histogram (b) of PtP1.4@Pt/C after acid etching treatment; (c) HRTEM image of PtP1.4@Pt/C (The inset shows the FFT pattern of the image); (d) XRD patterns of PtP1.4@Pt/C and commercial Pt/C.

Fig. 2. Structural and compositional characterization of PtP1.4@Pt/C. (a) HAADF-STEM image; (b)-(e) EELS mapping images; (f) Atomic models of PtP1.4@Pt; (g) EELS line-scanning profiles extracted from the boxed area in (e), showing that the Pt shell is ~1 nm thick.

Fig. 3. XPS of Pt 4f of PtP1.4@Pt/C and commercial Pt/C catalysts (a), and P 2p of PtP1.4@Pt/C (b).

Fig. 4. (a) ORR polarization curves of PtPx@Pt/C (x = 1.4, 0.5, and 0.06) and commercial Pt/C catalysts in an O2-saturated 0.1 M HClO4 solution, recorded at 10 mV s-1 at 30 °C; (b) CV curves in an Ar-saturated 0.1 M HClO4 solution at 50 mV s-1; (c) SA (solid bars) and MA (dashed bars) of the electrocatalysts for ORR at 0.90 V; (d) H2O2 yield (%H2O2) and electron transfer number (n) of ORR on Pt@PtP1.4/C.

Fig. 5. ORR polarization curves of PtP1.4@Pt/C (a) and Pt/C (b) before and after ADTs of potential cycling between 0.60 and 1.0 V; (c) ORR MAs at 0.90 V of the electrocatalysts before and after ADTs; (d) Loss of MAs for PtP1.4@Pt/C catalyst compared with reference results shown in Table S3.

Fig. 6. (a) Loss of ECSA for PtP1.4@Pt/C and commercial Pt/C after ADTs; TEM images of PtP1.4@Pt/C after ADTs of 30000 (b) and 90000 (c) potential cycles, and Pt/C after ADTs of 30000 potential cycles (d).

References

[1]	Y. Bing, H. Liu, L. Zhang, D. Ghosh, J. Zhang, Chem. Soc. Rev., 2010, 39, 2184-2202.
[2]	B. A. Lu, N. Tian, S. G. Sun, Curr. Opin. Electrochem., 2017, 4, 76-82.
[3]	R. Borup, J. Meyers, B. Pivovar, Y. S. Kim, R. Mukundan, N. Garland, D. Myers, M. Wilson, F. Garzon, D. Wood, P. Zelenay, K. More, K. Stroh, T. Zawodzinski, J. Boncella, J. E McGrath, M. Inaba, K. Miyatake, M. Hori, K. Ota, Z. Ogumi, S. Miyata, A. Nishikata, Z. Siroma, Y. Uchimoto, K. Yasuda, K. i. Kimijima, N. Iwashita, Chem. Rev., 2007, 107, 3904-3951.
[4]	Y. J. Wang, N. N. Zhao, B. Z. Fang, H. Li, X. T. T Bi, H. J. Wang, Chem. Rev., 2015, 115, 3433-3467.
[5]	X. Tian, X. Zhao, Y. Q. Su, L. Wang, H. Wang, D. Dang, B. Chi, H. Liu, E. J. M Hensen, X. W. D. Lou, B.Y. Xia, Science, 2019, 366, 850-856.
[6]	S. Wang, L. Xiong, J. Bi, X. Zhang, G. Yang, S. Yang, ACS Appl. Mater. Interfaces, 2018, 10, 27009-27018.
[7]	B. A. Lu, T. Sheng, N. Tian, Z. C. Zhang, C. Xiao, Z. M. Cao, H. B. Ma, Z. Y. Zhou, S. G. Sun, Nano Energy, 2017, 33, 65-71.
[8]	J. Kim, Y. Lee, S.h. Sun, J. Am. Chem. Soc., 2010, 132, 4996-4997.
[9]	V. Mazumder, M. Chi, K. L. More, S. Sun, J. Am. Chem. Soc., 2010, 132, 7848-7849.
[10]	L. Z. Bu, N. Zhang, S. J. Guo, X. Zhang, J. Li, J. L. Yao, T. Wu, G. Lu, J. Y. Ma, D. Su, X. Q. Huang, Science, 2016, 354, 1410-1414.
[11]	K. Jiang, D. Zhao, S. Guo, X. Zhang, X. Zhu, J. Guo, G. Lu, X. Huang, Sci. Adv., 2017, 3, 1601705.
[12]	X. Q. Huang, Z. P. Zhao, L. Cao, Y. Chen, E. B. Zhu, Z. Y. Lin, M. F. Li, A. M. Yan, A. Zettl, Y. M. Wang, X. F. Duan, T. Mueller, Y. Huang, Science, 2015, 348, 1230-1234.
[13]	V. R. Stamenkovic, B. Fowler, B. S. Mun, G. Wang, P. N. Ross, C. A. Lucas, N. M. Marković, Science, 2007, 315, 493-497.
[14]	S. Li, Z. Q. Tian, Y. Liu, Z. Jang, S. W. Hasan, X. Chen, P. Tsiakaras, P. K. Shen, Chin. J. Catal., 2021, 42, 648-657.
[15]	J. A. Gilbert, N. N. Kariuki, R. Subbaraman, A. J. Kropf, M. C. Smith, E. F. Holby, D. Morgan, D. J. Myers, J. Am. Chem. Soc., 2012, 134, 14823-14833.
[16]	J. Huang, C. Ding, Y. Yang, G. Liu, W. B. Cai, Chin. J. Catal., 2019, 40, 1895-1903.
[17]	Y. Shao, G. Yin, Y. Gao, P. Shi, J. Electrochem. Soc., 2006, 153, A1093-A1097.
[18]	J. Li, Z. Xi, Y. T. Pan, J. S. Spendelow, P. N. Duchesne, D. Su, Q. Li, C. Yu, Z. Yin, B. Shen, Y. S. Kim, P. Zhang, S. Sun, J. Am. Chem. Soc., 2018, 140, 2926-2932.
[19]	J. Liang, Z. Miao, F. Ma, R. Pan, X. Chen, T. Wang, H. Xie, Q. Li, Chin. J. Catal., 2018, 39, 583-589.
[20]	Y. H. Wen, R. Huang, C. Li, Z. Z. Zhu, S. G. Sun, J. Mater. Chem., 2012, 22, 7380-7386.
[21]	Q. Xu, W. Chen, Y. Yan, Z. Wu, Y. Jiang, J. Li, T. Bian, H. Zhang, J. Wu, D. Yang, Sci. Bull., 2018, 63, 494-501.
[22]	V. Beermann, M. Gocyla, E. Willinger, S. Rudi, M. Heggen, R. E Dunin Borkowski, M. G. Willinger, P. Strasser, Nano Lett., 2016, 16, 1719-1725.
[23]	K. Okaya, H. Yano, K. Kakinuma, M. Watanabe, H. Uchida, ACS Appl. Mater. Interfaces, 2012, 4, 6982-6991.
[24]	L. Dubau, J. Nelayah, T. Asset, R. Chattot, F. Maillard, ACS Catal., 2017, 7, 3072-3081.
[25]	T. Okada, Y. Ayato, M. Yuasa, I. Sekine, J. Phys. Chem. B, 1999, 103, 3315-3322.
[26]	K. Barbusiński, Ecolog. Chem. Eng. S, 2009, 16, 347-358.
[27]	M. Wang, X. Qin, K. Jiang, Y. Dong, M. Shao, W. B. Cai, J. Phys. Chem. C, 2017, 121, 3416-3423.
[28]	J. Li, J. Chen, Q. Wang, W. B. Cai, S. Chen, Chem. Mater., 2017, 29, 10060-10067.
[29]	A. R. J Kucernak, K. F. Fahy, V. N. N. Sundaram, Catal. Today, 2016, 262, 48-56.
[30]	Y. Xiong, Y. Ma, L. Zou, S. Han, H. Chen, S. Wang, M. Gu, Y. Shen, L. Zhang, Z. Xia, J. Li, H. Yang, J. Catal., 2020, 382, 247-255.
[31]	L. Zhang, M. Wei, S. Wang, Z. Li, L.X. Ding, H. Wang, Chem. Sci., 2015, 6, 3211-3216.
[32]	L. Feng, H. Xue, ChemElectroChem, 2017, 4, 20-34.
[33]	M. V. Gerasimov, Y. N. Simirskii, Metallurgist, 2008, 52, 477-481.
[34]	A. R. J Kucernak, V. N. Naranammalpuram Sundaram, J. Mater. Chem. A, 2014, 2, 17435-17445.
[35]	Y. R. Luo, Comprehensive Handbook of Chemical Bond Energies, CRC Press, 2007, 965.
[36]	B. A. Lu, L. F. Shen, J. Liu, Q. H. Zhang, L. Y. Wan, D. J. Morris, R. X. Wang, Z. Y. Zhou, G. Li, T. Sheng, L. Gu, P. Zhang, N. Tian, S. G. Sun, ACS Catal., 2020, 11, 355-363.
[37]	S. Suzuki, Y. Ohbu, T. Mizukami, Y. Takamori, M. Morishima, H. Daimon, M. Hiratani, J. Electrochem. Soc., 2009, 156, B27-B31.
[38]	M. Jiang, L. Ma, M. Gan, L. Hu, H. He, F. Xie, H. Zhang, Electrochim. Acta, 2019, 293, 30-39.
[39]	R. Guo, W. Bi, K. Zhang, Y. Liu, C. Wang, Y. Zheng, M. Jin, Chem. Mater., 2019, 31, 8205-8211.
[40]	W. Tian, Y. W. Wang, W. W. Fu, J. F. Su, H. Zhang, Y. Wang, J. Mater. Chem. A, 2020, 8, 20463-20473.
[41]	K. D. Jensen, J. Tymoczko, J. Rossmeisl, A. S. Bandarenka, I. Chorkendorff, M. Escudero Escribano, I. E. L. Stephens, Angew. Chem. Int. Ed., 2018, 57, 2800-2805.
[42]	D. Y. Chung, S. W. Jun, G. Yoon, S. G. Kwon, D. Y. Shin, P. Seo, J. M. Yoo, H. Shin, Y. H. Chung, H. Kim, B. S. Mun, K. S. Lee, N. S. Lee, S. J. Yoo, D. H. Lim, K. Kang, Y. E. Sung, T. Hyeon, J. Am. Chem. Soc., 2015, 137, 15478-15485.
[43]	H. Li, P. Wen, D. S. Itanze, Z. D. Hood, S. Adhikari, C. Lu, X. Ma, C. Dun, L. Jiang, D. L. Carroll, Y. Qiu, S. M. Geyer, Nat. Commun., 2020, 11, 3928.