Simultaneously achieving ultrahigh loading and ultrasmall particle size of Pt/C catalysts

doi:10.1016/S1872-2067(25)64673-0

Abstract

Abstract:

High-loading Pt/C catalysts play an important role in the fabrication of membrane electrode assemblies with thin catalytic layer, which enhance mass transport and maintain the balance of water and heat. Unfortunately, as the loading increases, the agglomeration and growth of Pt nanoparticles (NPs) occur, causing unsatisfactory performance. Here, we present an efficient method for preparing of highly dispersed and small-sized Pt/C catalysts with Pt loadings varying from 39.01 wt% to 66.48 wt% through the high-temperature shock technique. The high density and ultrafine (~2.5 nm) Pt NPs are successfully anchored onto Vulcan XC-72R carbon black without the use of additional capping agents or surfactants. The modified carbon supports enhance the affinity for Pt precursors, contributing to loading efficiencies of 95% or more, while also providing abundant sites for the nucleation and fixation of Pt NPs, thus preventing agglomeration. In the context of the hydrogen evolution reaction in acidic media, the as-synthesized high-loading Pt/C catalysts show remarkable activity and stability, outperforming the state-of-the-art commercial Pt/C. This is mainly because the combined effects of ultrasmall and uniform Pt NPs, optimized electronic structure of Pt site, superhydrophilicity and effective anchoring of Pt NPs. The polymer electrolyte membrane electrolyzer integrated with Pt60/OX72R and commercial IrO₂ reaches 1 A cm^-2 at 1.77 V and operates stably for 120 hours with a negligible voltage decay. This new strategy is fast, scalable and cost-effective for large-scale production of metal-supported catalysts, especially for the high-loading ones.

Key words: Pt/C catalyst, Ultrahigh loading, Ultrasmall size, High-temperature shock, Proton exchange membrane water electrolysis

Xiaoyang Wang, Ziqi Fu, Ziyi Luo, Weidi Liu, Jia Ding, Jianrong Zeng, Yanan Chen, Wenbin Hu. Simultaneously achieving ultrahigh loading and ultrasmall particle size of Pt/C catalysts[J]. Chinese Journal of Catalysis, 2025, 74: 425-437.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64673-0

https://www.cjcatal.com/EN/Y2025/V74/I7/425

Figures/Tables 5

Fig. 1. Preparation and characterization of carbon supports and Pt/C catalysts. High-resolution C 1s spectra (a) and Raman spectra (b) of 72R and OX-72R. TEM images of 72R (c) and OX-72R (d). (e) Schematic illustration of the synthetic procedure of high-loading Pt/C catalysts. (f) The temporal evolution of temperature during the HTS process. TEM images of the Pt40/OX72R (g), Pt40/72R (h), and TF-Pt40/OX72R (i). (j) TGA curves of the Pt40/OX72R and Pt40/72R tested under air atmosphere

Fig. 2. Morphology and microstructure characterization of Pt50/OX72R. (a) SEM images. (b) Magnifying SEM image. TEM images at low (c) and high (d) magnifications, and corresponding particle size distribution (e). (f) HRTEM image. STEM image (g) and corresponding EDX elemental mapping (h) of Pt. (i) TGA curves.

Fig. 3. Physical and chemical characterizations of Pt50/OX72R and Pt50/72R. (a) XRD patterns. (b) N2 gas adsorption-desorption isotherm curves (inset: corresponding pore size distributions). (c) Comparison of specific surface areas and pore volumes of the 72R and OX-72R before and after Pt loading. High-resolution XPS spectra of Pt 4f (d) and O 1s (e). (f) Fourier transform of k2-weighted EXAFS spectra. (g) PDF spectra and the fitting results. The inset is a schematic diagram of the first four atom-pairs in the unit cell, which corresponds to the first four PDF peaks. The right part is the local enlargement. (h) Photos showing the dynamic wettability.

Fig. 4. Electrocatalytic HER performance of Pt/C catalysts in 0.5 mol L-1 H2SO4 solution. (a) LSV curves with iR-compensation. (b) Comparative overpotentials at 10 mA cm-2 and 100 mA cm-2. (c) Tafel slopes. (d) Cdl values. (e) EIS Nyquist plots. (f) Chronopotentiometry curves at multistep current densities of 10, 50, and 100 mA cm-2.

Fig. 5. PEMWE performance characterization. (a) Photograph of the PEMWE device. (b) Polarization curves of the PEM electrolyzer obtained at 60 °C with Nafion 115 membrane. No cell voltages were iR compensated. (c) Chronopotentiometry curves of the PEM electrolyzer under the current density of 1 A cm-2.

References

[1]	Z.-Y. Wu, F.-Y. Chen, B. Li, S.-W. Yu, Y. Finfrock, D. Meira, Q.-Q. Yan, P. Zhu, M.-X. Chen, T.-W. Song, Z. Yin, H.-W. Liang, S. Zhang, G. Wang, H. Wang, Nat. Mater., 2022, 22, 100-108.
[2]	Z. Shi, Z. Wang, H. Wu, M. Xiao, C. Liu, W. Xing, Chin. J. Catal., 2024, 66, 223-232.
[3]	Q. Zhang, H. Chen, L. Yang, X. Liang, L. Shi, Q. Feng, Y. Zou, G.-D. Li, X. Zou, Chin. J. Catal., 2022, 43, 885-893.
[4]	L. An, C. Wei, M. Lu, H. Liu, Y. Chen, G. Scherer, A. Fisher, P. Xi, Z. Xu, C. Yan, Adv. Mater., 2021, 33, 2006328.
[5]	N. Zhang, J. Du, N. Zhou, D. Wang, D. Bao, H. Zhong, X. Zhang, Chin. J. Catal., 2023, 53, 134-142.
[6]	C. Li, H. Lu, G. Ding, T. Ma, S. Liu, L. Zhang, G. Liao, Chin. J. Catal., 2024, 65, 174-184.
[7]	B. Jiang, S. Liu, L. Cheng, L. Zhou, H. Cui, M. Liu, M. Wen, C. Wang, W. Wang, S. Li, X. Sun, Int. J. Hydrogen Energy, 2024, 58, 268-278.
[8]	R. Zhang, Y. Li, X. Zhou, A. Yu, Q. Huang, T. Xu, L. Zhu, P. Peng, S. Song, L. Echegoyen, F.-F. Li, Nat. Commun., 2023, 14, 2460.
[9]	W. Geng, X. Song, Z. Wei, M. Cao, R. Cao, ACS Appl. Energy Mater., 2022, 5, 15597-15604.
[10]	J. Fan, M. Chen, Z. Zhao, Z. Zhang, S. Ye, S. Xu, H. Wang, H. Li, Nat. Energy, 2021, 6, 475-486.
[11]	C. Xia, Y. Qiu, Y. Xia, P. Zhu, G. King, X. Zhang, Z. Wu, J. Kim, D.A. Cullen, D. Zheng, P. Li, M. Shakouri, E. Heredia, P. Cui, H. Alshareef, Y. Hu, H. Wang, Nat. Chem., 2021, 13, 887-894.
[12]	Y. Garsany, R. Atkinson, B. Gould, K. Swider-Lyons, J. Power Sources, 2018, 408, 38-45.
[13]	M. T. Anwar, X. Yan, M. R. Asghar, N. Husnain, S. Shen, L. Luo, X. Cheng, G. Wei, J. Zhang, Chin. J. Catal., 2019, 40, 1160-1167.
[14]	S. Li, H. Liu, Y. Wang, W. Xu, J. Li, Y. Liu, X. Guo, Y. Song, RSC Adv., 2015, 5, 8787-8792.
[15]	M. Rahman, K. Inaba, G. Batnyagt, M. Saikawa, Y. Kato, R. Awata, B. Delgertsetsega, Y. Kaneta, K. Higashi, T. Uruga, Y. Iwasawa, K. Ui, T. Takeguchi, RSC Adv., 2021, 11, 20601-20611.
[16]	F. Zheng, C. Zhang, X. Gao, C. Du, Z. Zhuang, W. Chen, Electrochim. Acta, 2019, 306, 627-634.
[17]	F. Wang, Q. Zhang, Z. Rui, J. Li, J. Liu, ACS Appl. Mater. Interfaces, 2020, 12, 30381-30389.
[18]	Z. Che, X. Lu, B. Cai, X. Xu, J. Bao, Y. Liu, Nano Res., 2021, 15, 1269-1275.
[19]	T. Ishida, T. Murayama, A. Taketoshi, M. Haruta, Chem. Rev., 2019, 120, 464-525.
[20]	C. A. Teles, C. Ciotonea, A. L. Valant, C. Canaff, J. Dhainaut, J.-M. Clacens, F. B. Noronha, F. Richard, S. Royer, Appl. Catal. B, 2023, 338, 123030.
[21]	A. Wang, L. Zhang, X. Li, Y. Gao, N. Li, G. Lu, L. Ge, Chin. J. Catal., 2022, 43, 1295-1305.
[22]	R. Zeng, K. Wang, W. Shao, J. Lai, S. Song, Y. Wang, Chin. J. Catal., 2020, 41, 820-829.
[23]	T. Yoo, J. Yoo, A. Sinha, M. Bootharaju, E. Jung, H. Lee, B.-H. Lee, J. Kim, W. Antink, Y. Kim, J. Lee, E. Lee, D. Lee, S.-P. Cho, S. Yoo, Y.-E. Sung, T. Hyeon, J. Am. Chem. Soc., 2020, 142, 14190-14200.
[24]	Y. Yuan, F. Zhang, H. Wang, J. Liu, Y. Zheng, S. Hou, RSC Adv., 2017, 7, 30542-30547.
[25]	S. Joo, K. Kwon, D. You, C. Pak, H. Chang, J. Kim, Electrochim. Acta, 2009, 54, 5746-5753.
[26]	Y. Li, X. Zhu, Y. Chen, S. Zhang, J. Li, J. Liu, J. Energy Chem., 2020, 47, 138-145.
[27]	F. Sun, R. Su, Y. Zhou, H. Li, F. Meng, Y. Luo, S. Zhang, W. Zhang, B. Zha, S. Zhang, F. Huo, ACS Appl. Mater. Interfaces, 2022, 14, 41079-41085.
[28]	Y. Hu, L. Xiang, L. Kuai, Y. Zhao, S. Cao, L. Liu, C. Fang, B. Geng, ACS Mater. Lett., 2023, 5, 2256-2262.
[29]	Y. Qiao, Y. Liu, Y. Liu, Q. Dong, G. Zhong, X. Wang, Z. Liu, X. Wang, S. He, W. Zhou, G. Wang, C. Wang, L. Hu, Small Methods, 2020, 4, 2000265.
[30]	H. Xie, Y. Liu, N. Li, B. Li, D. Kline, Y. Yao, M. Zachariah, G. Wang, D. Su, C. Wang, L. Hu, Nano Energy, 2021, 80, 105536.
[31]	Y. Liu, X. Tian, Y.-C. Han, Y. Chen, W. Hu, Chin. J. Catal., 2023, 48, 66-89.
[32]	X. Cui, Y. Liu, X. Wang, X. Tian, Y. Wang, G. Zhang, T. Liu, J. Ding, W. Hu, Y. Chen, ACS Nano, 2024, 18, 2948-2957.
[33]	Y. Qiao, C. Chen, Y. Liu, Y. Liu, Q. Dong, Y. Yao, X. Wang, Y. Shao, C. Wang, L. Hu, Nano Lett., 2021, 21, 4517-4523.
[34]	J. Kim, J. Cheon, T. Shin, J. Park, S. Joo, Carbon, 2016, 101, 449-457.
[35]	X. Luo, P. Yuan, J. Luo, H. Xiao, J. Li, H. Zheng, B. Du, D. Li, Y. Chen, Nanomaterials, 2023, 13, 1415.
[36]	Z. Li, X. Yang, N. Tsumori, Z. Liu, Y. Himeda, T. Autrey, Q. Xu, ACS Catal., 2017, 7, 2720-2724.
[37]	B. Ravel, M. Newville, J. Synchrotron Radiat., 2005, 12, 537-541.
[38]	P. Juhás, T. Davis, C. Farrow, S. Billinge, J. Appl. Crystallogr., 2013, 46, 560-566.
[39]	C. Farrow, P. Juhas, J. Liu, D. Bryndin, E. Božin, J. Bloch, T. Proffen, S. Billinge, J. Phys.-Condens. Matter, 2007, 19, 335219.
[40]	K. Omann, R. Sharma, P. Morgen, S. Gyergyek, M. Larsen, S. Andersen, ACS Appl. Energy Mater., 2023, 6, 1294-1307.
[41]	B. Liu, H. Yao, W. Song, L. Jin, I. Mosa, J. Rusling, S. Suib, J. He, J. Am. Chem. Soc., 2016, 138, 4718-4721.
[42]	W.-J. Lee, S. Bera, C. Kim, E.-K. Koh, W.-P. Hong, S.-J. Oh, E. Cho, S.-H. Kwon, NPG Asia Mater., 2020, 12, 40.
[43]	M. Bikshapathi, S. Mandal, G. Mathur, A. Sharma, N. Verma, Ind. Eng. Chem. Res., 2011, 50, 13092-13104.
[44]	C. Mercado-Zúñiga, J. R. Vargas-García, M. A. Hernández-Pérez, M. Z. Figueroa-Torres, F. Cervantes-Sodi, L. M. Torres-Martínez, J. Alloys Compd., 2014, 615, S538-S541.
[45]	E. E. Ateia, O. Rabie, A. T. Mohamed, Eur. Phys. J. Plus, 2024, 139, 24.
[46]	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.
[47]	Q. Li, H. Zhu, L. Zheng, L. Fan, Y. Ren, J. Chen, J. Deng, X. Xing, Adv. Sci., 2016, 3, 1600108.
[48]	G. Tang, X. Zhao, S. Liu, D. Mei, C. Zhao, L. Li, Y. Wang, Adv. Funct. Mater., 2025, 35, 2412254.
[49]	X. Li, C. Hao, Y. Du, Y. Fan, M. Wang, N. Wang, R. Meng, X. Wang, Z. Xu, Z. Cheng, Chin. J. Catal., 2023, 55, 191-199.
[50]	H. Sun, B. Yao, Y. Han, L. Yang, Y. Zhao, S. Wang, C. Zhong, J. Chen, C. Li, M. Du, Adv. Energy Mater., 2024, 14, 2303563.