渣油衍生碳载PtCoNiFeCu高熵金属间化合物催化剂用于提升质子交换膜燃料电池性能

PtCoNiFeCu High-entropy Intermetallics Supported on Petroleum Residue-derived Carbon for Enhanced Proton Exchange Membrane Fuel Cell Performance

摘要

以渣油作为前驱体， 合成了一种富含π电子的氮掺杂多孔碳载体（NPPC）， 并将其负载PtCoNiFeCu高熵金属间化合物（HEI）用于氧还原反应（ORR）. 通过NPPC与Pt金属之间强烈的d-π相互作用， 结合载体的物理限域效应， 将高熵纳米颗粒的平均粒径严格控制在2.30 nm， 极大化了活性位点的暴露. 同时， 该相互作用还在合金内部诱导产生了显著的压缩晶格应变（2.3%）， 从而优化了金属d轨道电荷分布， 并调节了氧中间体的吸附能， 从而极大提升了催化剂的ORR性能.实验结果表明， 所制备的PtCoNiFeCu HEI/NPPC 催化剂的质量活性（MA）高达2.07 A/mg_Pt， 约为商业Pt/C的14倍. 在30000次加速耐久性测试（ADT）后， 其质量活性保留率仍高达87%. 此外， 该催化剂在H₂-air质子交换膜燃料电池（PEMFC）中以0.1 mg/cm²的阴极铂负载量实现了1.03 W/cm²的超高峰值功率密度， 且在30000次循环后， 功率损耗仅为10%. 本研究为制备高活性、 长寿命的质子交换膜燃料电池催化剂提供了一种简单有效的方法.

Abstract

Using petroleum residue as a precursor， a π-electron-rich nitrogen-doped porous carbon（NPPC） was synthesized and supported to anchor PtCoNiFeCu high-entropy intermetallics（HEI） for the oxygen reduction reaction（ORR）. Benefiting from the strongd-π interaction between NPPC and Pt， coupled with the physical confinement effect of the support， the average nanoparticle size was precisely restricted to 2.30 nm， maximizing the exposure of active sites. Concurrently， this interaction induces a significant compressive lattice strain（2.3%） within the alloy structure， optimizing the metal d-orbital charge distribution and tuning the adsorption energies of oxygen intermediates， which significantly enhances the ORR performance. Experimental results demonstrate that the as-prepared PtCoNiFeCu HEI/NPPC catalyst delivers a superior mass activity（MA） of 2.07 A/mg_Pt， approximately 14-fold higher than that of commercial Pt/C. Remarkably， the catalyst retains 87% of its initial MA after 30000 accelerated durability test（ADT） cycles. Furthermore， the catalyst achieves a peak power density of 1.03 W/cm² in H₂-air proton exchange membrane fuel cells（PEMFCs） at a low cathodic Pt loading of 0.1 mg/cm²， with a power loss of only 10% after 30000 cycles. This work provides a simple and effective strategy for the development of highly active and durable catalysts for PEMFCs through strategic support engineering.

关键词

多孔碳载体 / 晶格应变 / 高熵金属间化合物 / 质子交换膜燃料电池

Key words

Porous carbon support / Lattice strain / High-entropy intermetallic compound / Proton exchange membrane fuel cell

参考文献

[1] Yang C. L., Wang L. N., Yin P., Liu J., Chen M. X., Yan Q. Q., Wang Z. S., Xu S. L., Chu S. Q., Cui C., Science, 2021, 374(6566), 459-464

[2] Jiao K., Xuan J., Du Q., Bao Z., Xie B., Wang B., Zhao Y., Fan L., Wang H., Hou Z., Nature, 2021, 595(7867), 361-369

[3] Li L., Tang X., Wu B., Huang B., Yuan K., Chen Y., Adv. Mater., 2024, 36(13), 2308326

[4] Luo B., Zhou F., Pan M. , Chem. J. Chinese Universities, 2022, 43(4), 20210853

[5] (罗昪, 周芬, 潘牧 . 高等学校化学学报, 2022, 43(4), 20210853)

[6] Zhao Q., Li S., Chen K. W., Wen Z. Y., Zhang X. Y., Yi S. J., Pan M. , Chem. J. Chinese Universities, 2023, 44(6), 20230016

[7] (赵倩, 李赏, 程矿伟, 文智勇, 张晓宇, 易少杰, 潘牧 . 高等学校化学学报, 2023, 44(6), 20230016)

[8] Gui R., Cheng H., Wang M., Tai X., Zhang H., Liu C., Cao X., Chen C., Ge M., Wang H., Adv Mater., 2024, 36(11), 2307661

[9] Wang E., Luo L., Feng Y., Wu A., Li H., Luo X., Guo Y., Tan Z., Zhu F., Yan X., J. Energy Chem., 2024, 93, 157-165

[10] Hu S. N., Xu W. C., Tian N., Chen S. M., Li M. Y., Shen J. F., Lin J. X., Guo S. L., Huang X. Y., Zhou Z. Y., Energy Environ. Sci., 2024, 17(9), 3099-3111

[11] Li J., Sharma S., Liu X., Pan Y. T., Spendelow J. S., Chi M., Jia Y., Zhang P., Cullen D. A., Xi Z., Joule, 2019, 3(1), 124-135

[12] Li J., Sharma S., Wei K., Chen Z., Morris D., Lin H., Zeng C., Chi M., Yin Z., Muzzio M., J. Am. Chem. Soc., 2020, 142(45), 19209-19216

[13] Niu M., Guan Q., Yuan W., Guo C. X., Cao D., Li C. M., Zhang L. Y., Zhao X. S., Chem. Eng. J., 2025, 503, 158465

[14] Wang Y., Gong N., Liu H., Ma W., Hippalgaonkar K., Liu Z., Huang Y., Adv. Mater., 2023, 35(28), 2302067

[15] Luan T., Zhao J., Gao T., Wang F., Xu H., Song Z., Luo L., Gong S., Liu B., Adv. Funct. Mater., 2025, 35(44), 2506851

[16] Qin P., Liu D., Li C., Peng G., Waterhouse G. I., Han Y., Shui J., Luo M., Shang L., Guo S., J. Am. Chem. Soc., 2026, 148(9), 9563-9571

[17] Lu J., Luo L., Yin S., Hasan S. W., Tsiakaras P., ACS Sustainable Chem. Eng., 2019, 7(19), 16209-16214

[18] Qiu Y., Rao Y., Zheng Y., Hu H., Zhang W., Guo X., InfoMat, 2022, 4(9), e12326

[19] Zhang J., Liang P., Xu X., Wang R., Liu S., Wang C., Liu B., Luo L., Jin M., Liu H., Nano Mater. Sci., 2024, 7(1), 105-112

[20] He X., Zhang N., Shao X., Wu M., Yu M., Qiu J., Chem. Eng. J., 2016, 297, 121-127

[21] Jalilov A. S., Li Y., Tian J., Tour J. M., Adv. Energy Mater., 2017, 7(1), 1600693

[22] Xu R., Yi Z., Song M., Chen J., Wei X., Su F., Dai L., Sun G., Yang F., Xie L., Carbon, 2023, 206, 94-104

[23] Wan K., Luo C., Wang J., Xu W., Pei X., Zhou X., Ming P., Liang H., Li B., eScience, 2025, 100510

[24] Gao H., Wang S., Cheong W. C., Wang K., Xu H., Huang A., Ma J., Li J., Ip W. F., San Hui. K., Carbon, 2023, 203, 76-87

[25] Ramaswamy N., Tylus U., Jia Q., Mukerjee S., J. Am. Chem. Soc., 2013, 135(41), 15443-15449

[26] Jiao L., Wan G., Zhang R., Zhou H., Yu S. H., Jiang H. L., Angew. Chem., 2018, 130(28), 8661-8665

[27] Song T. W., Zuo L. J., Zuo M., Liang H. W., J. Catal., 2023, 419, 19-25

[28] Zhang L., Tong L., Li S., Ma C. S., Xue K. Z., Liang H. W., J. Energy Chem., 2025, 101, 1-6

[29] Kwon T., Kim T., Son Y., Lee K., Adv. Energy Mater., 2021, 11(22), 2100265

[30] Lu B. A., Shen L. F., Liu J., Zhang Q., Wan L. Y., Morris D. J., Wang R. X., Zhou Z. Y., Li G., Sheng T., ACS Catal., 2020, 11(1), 355-363

[31] Song T. W., Chen M. X., Yin P., Tong L., Zuo M., Chu S. Q., Chen P., Liang H. W., Small, 2022, 18(31), 2202916

[32] Li J., Li L., Lin W., Chen X., Yang W., ACS Sustainable Chem. Eng., 2024, 12(13), 5241-5250

基金资助

中国石油化工集团公司项目(421100-2)