WN增强金属-N-C载体平台构筑燃料电池用高耐久性Pt基氧还原催化剂

doi:10.1016/S1872-2067(26)65108-X

摘要/Abstract

摘要：

质子交换膜燃料电池(PEMFC)功率密度高, 产物只有水, 被视为最理想的能源动力系统之一. 然而, 其阴极氧还原(ORR)反应动力学缓慢, 需要高活性铂(Pt)基催化剂以维持高能量输出, 成本居高难下. 同时, 催化剂在实际运行中易因碳载体腐蚀、Pt纳米颗粒团聚及金属溶解等问题而性能迅速衰减. PEMFC的应用长期面临ORR催化剂在活性、耐久性与成本之间难以兼顾的“不可能三角”困境. 针对上述挑战, 本文创新提出“氮化钨增强金属-氮-碳(WN-M-N-C) ”载体策略, 通过引入亚纳米WN与原子级分散的金属-Nₓ位点协同作用, 同步优化Pt的电子结构与催化界面的稳定性.

关键词: 氧还原反应, 耐久性, 活性, 氮化钨, 金属-氮-碳, 质子交换膜燃料电池

Abstract:

The widespread deployment of proton exchange membrane fuel cells is hindered by the “catalysis trilemma” of the oxygen reduction reaction (ORR), which demands simultaneous high activity, exceptional durability and low cost. To overcome this longstanding bottleneck, we propose a universal tungsten nitride (WN) enhanced metal-N-C platform, where WN synergizes with metal-N_x sites to create a robust and electronically modulated support for Pt catalysts. This dual-anchoring and synergistic-catalyzing architecture not only effectively suppresses Pt nanoparticle migration and dissolution but also optimizes Pt activity, thereby accelerating ORR kinetics and enhancing structural integrity. As a prototypical example, the Pt/WN-Fe-N-C catalyst delivers a remarkable peak power density of 1.85 W/cm² at an ultralow cathode Pt loading of 0.05 mg-_Pt/cm² and retains 91.1% peak power density after 90000 accelerated durability test cycles with 4 mV voltage loss at 0.80 A/cm²-significantly exceeding the U.S. DOE 2030 targets. This work establishes a generalizable materials design strategy to break the activity-stability-cost trade-off in fuel cell catalysis.

Key words: Oxygen reduction reaction, Durability, Activity, Tungsten nitride, Metal-N-C, Proton exchange membrane fuel cells

李柯, 罗燚, 蔡晨宁, 郑泽民, 余罡, 胡建强, 陈胜利. WN增强金属-N-C载体平台构筑燃料电池用高耐久性Pt基氧还原催化剂[J]. 催化学报, 2026, 87: 230-242.

Ke Li, Yi Luo, Chenning Cai, Zemin Zheng, Gang Yu, Jianqiang Hu, Shengli Chen. WN enhanced metal-N-C platform for ultra-stable Pt oxygen reduction electrocatalyst in fuel cell[J]. Chinese Journal of Catalysis, 2026, 87: 230-242.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65108-X

https://www.cjcatal.com/CN/Y2026/V87/I8/230

图/表 5

Fig. 1. Overall performance demonstration and structural characterizations of the developed catalysts. (a) Schematic illustration of the microstructure of Pt/WN-M-N-C catalysts. (b) XRD patterns of Pt/WN-M-N-C catalysts with different metals (M = Fe/Co/Ni), as well as those of TKK 20% Pt/C and WN-Fe-N-C. (c) HAADF-STEM image of WN-Fe-N-C. Elemental mapping of WN-Fe-N-C: corresponding HAADF-STEM image (d), W (e), N (f), and Fe (g). (h) HAADF-STEM image of Pt/WN-Fe-N-C with the corresponding Pt nanoparticle size distribution histogram. Comparison diagram of durability data between Pt/W-Fe-N-C and other recently reported advanced Pt-based catalysts in MEA: MA retention (i) and peak power density retention (j) [1,39-59].

Fig. 2. Comprehensive microstructural and electronic characterization of the Pt/WN-Fe-N-C catalyst. (a) Bright-field TEM image revealing the triphasic interface between Pt nanocrystals, carbon matrix, and WN nanoparticles. (b) High-magnification HAADF-STEM image of a single Pt nanoparticle demonstrating the well-ordered atomic arrangement characteristic of high crystallinity. (c?f) Atomic-resolution HAADF-STEM image of an individual Pt-based nanoparticle. (d) Corresponding elemental maps of the nanoparticle displayed in panel (c): Pt-L signal (d), Fe-K signal (e), and W-L signal (f). (g) Elemental line-scan profile across the nanoparticle indicated in panel (c), showing the spatial distribution of Pt, Fe, and W. (h) High-resolution Pt 4f XPS spectra with peak deconvolution for Pt/WN-Fe-N-C, Pt-Fe/Fe-N-C, and commercial TKK 20% Pt/C. (i) High-resolution W 4f XPS spectra with corresponding peak fitting analysis for Pt/WN-Fe-N-C and WN-Fe-N-C.

Fig. 3. Comparative electrochemical stability evaluation of Pt/WN-M-N-C (M = Fe, Co, Ni) catalysts under different aging cycles. CV curves (a), LSV curves (b), and performance degradation data (c) of Pt/WN-Fe-N-C at different numbers of aging cycles. CV curves (d), LSV curves (e), and performance degradation data (f) of Pt/WN-Co-N-C at different numbers of aging cycles. CV curves (g), LSV curves (h), and performance degradation data (i) of Pt/WN-Ni-N-C at different numbers of aging cycles. Test conditions: 25 °C, oxygen saturated 0.10 mol/L HClO4 solution, 20 mV/s for CV test, 1600 rpm for LSV test, 15 µg/cm2-Pt loading on the electrode, ADT cycles between 0.60-1.00 V vs. RHE at 50 mV/s.

Fig. 4. The TEM images and Pt nanoparticle size distribution histogram of Pt/WN-M-N-C. The TEM images of Pt/WN-Fe-N-C (a), Pt/WN-Co-N-C (b), and Pt/WN-Ni-N-C (c) after ADTs. Pt nanoparticle size distribution histogram of Pt/WN-Fe-N-C (d), Pt/WN-Co-N-C (e), and Pt/WN-Ni-N-C (f) before and after ADTs.

Fig. 5. Performance evaluation of PEMFC with Pt/WN-Fe-N-C and TKK50% Pt/C catalysts under various ADT cycles. (a) Polarization curves of H2-O2 MEAs with Pt/WN-Fe-N-C as cathode catalyst at different ADT cycles. (b) Peak power density and MA data of H2-O2 MEAs with Pt/WN-Fe-N-C cathode catalyst at different ADT cycles. (c) CV curves of PEM fuel cells at different ADT cycles using Pt/WN-Fe-N-C as cathode catalyst. (d) Polarization curves of H2-O2 MEAs with TKK 50% Pt/C cathode catalyst. (e) Voltage values at 0.80 A/cm2 current density under various ADT cycles (H2-O2 Pt-Fe/Fe-N-C in Ref. [28]). Test conditions: 0.05 mg/cm2 Pt loading for Pt/WN-Fe-N-C, 0.100 mg/cm2 Pt loading for TKK Pt/C, back pressure 150 kPa, 80 °C, 100% R.H. (f) TEM of Pt/WN-Fe-N-C after 90000 cycles ADTs in MEA.

参考文献

[1]	Z. Liu, B. Peng, Y. J. Tsai, A. Zhang, M. Xu, W. Zang, X. Yan, L. Xing, X. Pan, X. Duan, Y. Huang, Nat. Nanotechnol., 2025, 20, 807-814.
[2]	X. Cao, H. Guo, Y. Han, M. Li, C. Shang, R. Zhao, Q. Huang, M. Li, Q. Zhang, F. Lv, H. Tan, Z. Qian, M. Luo, S. Guo, Nat. Commun., 2025, 16, 2851.
[3]	G. Wu, P. Zelenay, Nat. Rev. Mater., 2024, 9, 643-656.
[4]	T. Ioroi, Z. Siroma, S.-I. Yamazaki, K. Yasuda, Adv. Energy Mater., 2019, 9, 1801284.
[5]	S. Zhang, M. Chen, X. Zhao, J. Cai, W. Yan, J. C. Yen, S. Chen, Y. Yu, J. Zhang, Electrochem. Energy Rev., 2021, 4, 336-381.
[6]	Y. Chen, J. Chen, J. Zhang, Y. Xue, G. Wang, R. Wang, Inorg. Chem., 2022, 61, 5148-5156.
[7]	Y. Zhang, Q. Zhao, B. Danil, W. Xiao, X. Yang, Adv. Mater., 2024, 36, 2400198.
[8]	S. Li, G. Wang, H. Lv, Z. Lin, J. Liang, X. Liu, Y.-G. Wang, Y. Huang, G. Wang, Q. Li, J. Am. Chem. Soc., 2024, 146, 17659-17668.
[9]	X. Tian, J. Luo, H. Nan, H. Zou, R. Chen, T. Shu, X. Li, Y. Li, H. Song, S. Liao, R. R. Adzic, J. Am. Chem. Soc., 2016, 138, 1575-1583.
[10]	H. Prats, M. Stamatakis, J. Phys. Chem. Lett., 2024, 15, 3450-3460.
[11]	Y. Zhong, X. Xia, F. Shi, J. Zhan, J. Tu, H.-J. Fan, Adv. Sci., 2016, 3, 1500286.
[12]	D. Zhang, Q. Xiang, Mater. Lett., 2020, 278, 128411.
[13]	Y. Zhou, H. Xue, T. Wang, H. Guo, X. Fan, L. Song, W. Xia, H. Gong, Y. He, J. Wang, J. He, Chem. Asian J., 2017, 12, 60-66.
[14]	Y. Wu, Y. Zhao, J. Liu, F. Wang, J. Mater. Chem. A, 2018, 6, 10700-10709.
[15]	J. Liang, N. Li, Z. Zhao, L. Ma, X. Wang, S. Li, X. Liu, T. Wang, Y. Du, G. Lu, J. Han, Y. Huang, D. Su, Q. Li, Angew. Chem. Int. Ed., 2019, 58, 15471-15477.
[16]	Y. Du, W. Chen, Z. Zhong, S. Wang, L. Zhou, D. Xiong, Y. Liu, Z. Liu, K. Wang, J. Alloys Compd., 2023, 960, 170789.
[17]	X. Yao, Z. Song, X. Yao, Y. Guan, N. Hamada, J. Zhang, Z. Huo, L. Zhang, C. V. Singh, X. Sun, Angew. Chem. Int. Ed., 2024, 63, e202318872.
[18]	W. Tu, K. Chen, L. Zhu, H. Zai, E. Bin, X. Ke, C. Chen, M. Sui, Q. Chen, Y. Li, Adv. Funct. Mater., 2019, 29, 1807070.
[19]	B. Zhang, X. Zheng, O. Voznyy, R. Comin, M. Bajdich, M. Garcia-Melchor, L. Han, J. Xu, M. Liu, L. Zheng, F. P. Garcia de Arquer, C. T. Dinh, F. Fan, M. Yuan, E. Yassitepe, N. Chen, T. Regier, P. Liu, Y. Li, P. De Luna, A. Janmohamed, H. L. Xin, H. Yang, A. Vojvodic, E. H. Sargent, Science, 2016, 352, 333-337.
[20]	Y. Ma, H. Guo, H. Xue, T. Wang, L. Li, H. Gong, X. Fan, L. Song, B. Gao, W. Xia, C. Jiang, J. He, J. Porous Mater., 2020, 27, 719-726.
[21]	Y. Du, W. Chen, L. Zhou, R. Hu, S. Wang, X. Li, Y. Xie, L. Yang, Y. Liu, Z. Liu, Nano Res., 2023, 16, 8773-8781.
[22]	C. Zhang, H. Liu, C. Jin, H. Guo, Mater. Lett., 2021, 291, 129433.
[23]	J. Zhang, J. Chen, H. Yang, J. Fan, F. Zhou, Y. Wang, G. Wang, R. Wang, RSC Adv., 2017, 7, 33921-33928.
[24]	W. W. McNeary, S. F. Zaccarine, A. Lai, A. E. Linico, S. Pylypenko, A. W. Weimer, Appl. Catal. B, 2019, 254, 587-593.
[25]	S. Li, J. Liu, J. Liang, Z. Lin, X. Liu, Y. Chen, G. Lu, C. Wang, P. Wei, J. Han, Y. Huang, G. Wu, Q. Li, Appl. Catal. B, 2023, 320, 122017.
[26]	Y. Chen, Z. Meng, F. Liu, A. Zhang, X. Wang, Y. Xiong, H. Tang, T. Tian, H. Tang, Adv. Funct. Mater., 2024, 34, 2408383.
[27]	J. Guan, Y. Zan, R. Shao, J. Niu, M. Dou, B. Zhu, Z. Zhang, F. Wang, Small, 2020, 16, 2005048.
[28]	Y. Luo, K. Li, Y. Chen, J. Feng, L. Wang, Y. Jiang, L. Li, G. Yu, J. Feng, Adv. Mater., 2023, 35, 2300624.
[29]	Y. Luo, K. Li, Y. Hu, T. Chen, Q. Wang, J. Hu, J. Feng, J. Feng, Small, 2024, 20, 2309822.
[30]	Y. Luo, J. Wu, Y. Chen, J. Feng, L. Wang, L. Li, Y. Jiang, Y. Lei, J. Feng, Nano Energy, 2022, 104, 107869.
[31]	S. J. Tauster, Acc. Chem. Res., 1987, 20, 389-394.
[32]	D. Li, K. Gao, Z. Miao, Y. Miao, X. Wang, D. Wang, Z. Li, Y. Han, Q. Zheng, Z. Li, C. Sun, J. Colloid Interface Sci., 2025, 677, 1034-1044.
[33]	Z. Huang, B. Yang, Y. Zhou, W. Luo, G. Chen, M. Liu, X. Liu, R. Ma, N. Zhang, ACS Nano, 2023, 17, 25091-25100.
[34]	Y. He, S. Liu, C. Priest, Q. Shi, G. Wu, Chem. Soc. Rev., 2020, 49, 3484-3524.
[35]	S. Ji, Y. Chen, X. Wang, Z. Zhang, D. Wang, Y. Li, Chem. Rev., 2020, 120, 11900-11955.
[36]	A. Kumar, X. Liu, J. Lee, B. Debnath, A. R. Jadhav, X. Shao, V. Q. Bui, Y. Hwang, Y. Liu, M. G. Kim, H. Lee, Energy Environ. Sci., 2021, 14, 6494-6505.
[37]	Z. Chen, Y. Xu, D. Ding, G. Song, X. Gan, H. Li, W. Wei, J. Chen, Z. Li, Z. Gong, X. Dong, C. Zhu, N. Yang, J. Ma, R. Gao, D. Luo, S. Cong, L. Wang, Z. Zhao, Y. Cui, Nat. Commun., 2022, 13, 763.
[38]	C. Gyan-Barimah, J. S. P. Mantha, H.-Y. Lee, Y. Wei, C.-H. Shin, M. I. Maulana, J. Kim, G. Henkelman, J.-S. Yu, Nat. Commun., 2024, 15, 7034.
[39]	Z. Qiao, C. Wang, C. Li, Y. Zeng, S. Hwang, B. Li, S. Karakalos, J. Park, A. J. Kropf, E. C. Wegener, Q. Gong, H. Xu, G. Wang, D. J. Myers, J. Xie, J. S. Spendelow, G. Wu, Energy Environ. Sci., 2021, 14, 4948-4960.
[40]	Y.-T. Pan, D. Li, S. Sharma, C. Wang, M. J. Zachman, E. C. Wegener, A. J. Kropf, Y. S. Kim, D. J. Myers, A. A. Peterson, D. A. Cullen, J. S. Spendelow, Chem Catal., 2022, 2, 3559-3572.
[41]	F. Xiao, Q. Wang, G.-L. Xu, X. Qin, I. Hwang, C.-J. Sun, M. Liu, W. Hua, H.-W. Wu, S. Zhu, J.-C. Li, J.-G. Wang, Y. Zhu, D. Wu, Z. Wei, M. Gu, K. Amine, M. Shao, Nat. Catal., 2022, 5, 503-512.
[42]	Q. Cheng, S. Yang, C. Fu, L. Zou, Z. Zou, Z. Jiang, J. Zhang, H. Yang, Energy Environ. Sci., 2022, 15, 278-286.
[43]	S. Shin, E. Lee, J. Nam, J. Kwon, Y. Choi, B. J. Kim, H. C. Ham, H. Lee, Adv. Energy Mater., 2024, 14, 2400599.
[44]	Z. Zhao, Z. Liu, A. Zhang, X. Yan, W. Xue, B. Peng, H. L. Xin, X. Pan, X. Duan, Y. Huang, Nat. Nanotechnol., 2022, 17, 968-975.
[45]	S.-M. Chen, L.-K. Chen, N. Tian, S.-N. Hu, S.-L. Yang, J.-F. Shen, J.-X. Tang, D.-Y. Wu, M.-S. Chen, Z.-Y. Zhou, S.-G. Sun, ACS Catal., 2024, 14, 16664-16672.
[47]	S. Zhou, W. Bi, J. Zhang, L. He, Y. Yu, M. Wang, X. Yu, Y. Xie, C. Wu, Adv. Mater., 2024, 36, 2400808.
[48]	E. Lee, H. Jin, H. Jo, M.-G. Kim, J. H. Park, J. Baik, J. S. Park, J.-H. Jang, S.-H. Kim, D. W. Lee, J. Choi, J. K. Ryu, D. Choi, J. Kim, S. M. Kim, Y.-E. Sung, K.-S. Lee, D. Ahn, Y. Yang, D. W. Chun, S. J. Yoo, Adv. Mater., 2025, 37, 2504059.
[49]	J. Liang, H. Yu, M. J. Zachman, S. Hwang, M. Qi, Y. Zeng, B. Zhang, J. Li, J. Guo, C. Dun, N. MacAuley, G. Wu, Adv. Mater., 2025, https://doi.org/10.1002/adma.202510847.
[50]	J. Liang, Y. Wan, H. Lv, X. Liu, F. Lv, S. Li, J. Xu, Z. Deng, J. Liu, S. Zhang, Y. Sun, M. Luo, G. Lu, J. Han, G. Wang, Y. Huang, S. Guo, Q. Li, Nat. Mater., 2024, 23, 1259-1267.
[51]	B. Peng, Z. Liu, L. Sementa, Q. Jia, Q. Sun, C. U. Segre, E. Liu, M. Xu, Y.-H. Tsai, X. Yan, Z. Zhao, J. Huang, X. Pan, X. Duan, A. Fortunelli, Y. Huang, Nat. Catal., 2024, 7, 818-828.
[52]	S. Yin, Y.-N. Yan, L. Chen, N. Cheng, X. Cheng, R. Huang, H. Huang, B. Zhang, Y.-X. Jiang, S.-G. Sun, ACS Nano, 2024, 18, 551-559.
[53]	Y. Wu, L. Chen, S. Geng, Y. Tian, R. Chen, K. Wang, Y. Wang, S. Song, Adv. Funct. Mater., 2024, 34, 2307297.
[54]	H. Yan, M. Meng, L. Wang, A. Wu, C. Tian, L. Zhao, H. Fu, Nano Res., 2016, 9, 329-343.
[55]	X. Pan, X. Song, S. Lin, K. Bi, Y. Hao, Y. Du, J. Liu, D. Fan, Y. Wang, M. Lei, Ceram. Int., 2016, 42, 16017-16022.
[56]	Y. Yan, J. Lin, K. Huang, X. Zheng, L. Qiao, S. Liu, J. Cao, S. C. Jun, Y. Yamauchi, J. Qi, J. Am. Chem. Soc., 2023, 145, 24218-24229.
[57]	T. Yang, Y. Yan, R. Liu, K. Huang, R. Xu, J. Chen, J. Tu, S. Liu, L. Kang, Z. Wang, J. Cao, J. Qi, Nano Lett., 2025, 25, 7707-7715.
[58]	P. Ren, P. Pei, Y. Li, Z. Wu, D. Chen, S. Huang, Prog. Energy Combust. Sci., 2020, 80, 100859.
[59]	T. Dukić, L. Pavko, P. Jovanovič, N. Maselj, M. Gatalo, N. Hodnik, Chem. Commun., 2022, 58, 13832-13854.