通过Fe-N-C层介导的5d-3d/2p耦合增强Pt/C催化剂在质子交换膜燃料电池中氧还原反应的稳定性研究

doi:10.1016/S1872-2067(26)64985-6

催化学报 ›› 2026, Vol. 83: 308-318.DOI: 10.1016/S1872-2067(26)64985-6

通过Fe-N-C层介导的5d-3d/2p耦合增强Pt/C催化剂在质子交换膜燃料电池中氧还原反应的稳定性研究

庄玉娟^a^,^b, 陈庆军^a^,^b^,^*(), 林兴恩^a, 孟令伟^a, 胡富望^b, 余新涛^a, Geoffrey I. N. Waterhouse^c, 彭立山^a^,^b^,^*()

^a中国科学技术大学稀土学院, 安徽合肥 230026, 中国
^b中国科学院赣江创新研究院, 江西赣州 341119, 中国
^c奥克兰大学化学科学学院, 奥克兰, 新西兰

收稿日期:2025-07-25 接受日期:2025-09-01 出版日期:2026-04-18 发布日期:2026-03-04
通讯作者: * 电子信箱: qjchen@gia.cas.cn (陈庆军), lspeng@gia.cas.cn (彭立山).
基金资助:
国家自然科学基金(22209186);国家自然科学基金(22479149);江西省自然科学基金(20242BAB23016);江西省双千计划(jxsq2023101056);江西省重点研发项目(20223BBG74004);中国科学院青年创新促进会(2023343)

Enhancing the stability of Pt/C catalysts for oxygen reduction reaction in PEMFCs via Fe-N-C-mediated 5d-3d/2p orbital hybridization

Yujuan Zhuang^a^,^b, Qingjun Chen^a^,^b^,^*(), Xingen Lin^a, Lingwei Meng^a, Fuwang Hu^b, Xintao Yu^a, Geoffrey I. N. Waterhouse^c, Lishan Peng^a^,^b^,^*()

^aSchool of Rare Earths, University of Science and Technology of China, Hefei 230026, Anhui, China
^bKey Laboratory of Rare Earths, Ganjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou 341119, Jiangxi, China
^cSchool of Chemical Sciences, The University of Auckland, Auckland 1142, New Zealand

Received:2025-07-25 Accepted:2025-09-01 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: qjchen@gia.cas.cn (Q. Chen), lspeng@gia.cas.cn (L. Peng).
Supported by:
National Natural Science Foundation of China(22209186);National Natural Science Foundation of China(22479149);Natural Science Foundation of Jiangxi Province(20242BAB23016);"Double Thousand Plan" of Jiangxi Province(jxsq2023101056);Key Research and Development Program of Jiangxi Province(20223BBG74004);Youth Innovation Promotion Association, Chinese Academy of Sciences(2023343)

摘要/Abstract

摘要：

质子交换膜燃料电池(PEMFCs)具有能量密度高, 产物清洁等优点. 碳载铂(Pt/C)催化剂被广泛应用于PEMFCs的氧还原反应(ORR), 但存在活性和稳定性不足问题, 该催化剂在严苛的工作环境下容易发生溶解团聚, 甚至从载体上脱离. 此外, 裸露的铂纳米粒子容易受到磺酸基团、一氧化碳等物质毒化. 研究者已开发出铂过渡金属有序合金(PtM)来提高其稳定性, 但铂溶解的问题仍未得到根本解决. 此外, 将铂基纳米颗粒包裹在碳包覆层中可以保护金属免受外部反应环境的影响, 从而显著缓解了铂基纳米颗粒中毒和溶解问题. 然而, 碳层本身具有化学惰性, 且电子穿透能力有限(通常仅能穿透2-3层碳原子), 这在一定程度上阻碍反应物与活性位点的接触及电子传输, 对催化活性的充分发挥构成挑战.
本文采用Fe-N-C涂层(碳载体负载原子分散FeN_x位点)包覆Pt/C催化剂有望打破纯碳包覆层上电子分布的均匀性, 进而突破纯碳层的电子屏蔽效应. 此外, 内层Pt与Fe-N-C的强相互作用有望增强Fe-N-C的结构稳定性, 并保护内层Pt不受腐蚀和毒化. 基于此, 本文制备了一系列具有不同Fe-N-C含量包覆的PtFe/C@Fe-N-C催化剂. 结果表明, 具有合适Fe-N-C包覆厚度的PtFe/C@Fe-N-C催化剂在酸性介质中展现了卓越的ORR耐久性和催化性能: PtFe/C@Fe-N-C催化剂在0.1 mol L^‒1高氯酸溶液中, 其半波电位高达0.931 V, 在0.9 V电压下的质量活性(MA)高达1.02 A mg_Pt^‒1, 且经过30000圈加速耐久性测试(ADT)后仅衰减1.8%. 即使经历100000圈循环测试后, 该催化剂的MA仍为Pt/C催化剂初始质量活性(0.27 A mg_Pt^‒1)的三倍多, 而Pt/C催化剂和PtFe/C催化剂经过30000圈ADT后, MA分别衰减了53.4%和39.3%. 在实际的H₂-O₂ PEMFCs测试中, PtFe/C@Fe-N-C催化剂也展现出优异的活性和耐久性: 峰值功率密度高达2.03 W cm^‒2, 质量活性达到0.75 A mg_Pt^‒1, 经过30000次循环实验后, 其MA仅下降2.7%, 远优于Pt/C催化剂的初始活性(0.176 A mg_Pt^‒1, 1.35 W cm^‒2)和稳定性(MA衰减54%), 这远超美国能源部(DOE)2025年设定的指标. 理论计算结果表明, Pt与表面FeN_x位之间的5d-3d/2p轨道强耦合作用改变了表面FeN_x位点的电子结构, 优化ORR中间体的吸附能, 同时提高了表面Fe原子的溶解能垒, 最终提升了PtFe/C@Fe-N-C催化剂在ORR过程中的活性和长期稳定性.
综上, 本研究利用Fe-N-C层包覆铂基催化剂, 使得催化剂在实际燃料电池运行条件下展示出卓越的耐久性和活性, 并通过实验和理论计算阐明了催化剂稳定性和活性提升的机制. 本研究为下一代电催化剂的发展提供了清晰的设计思路与实施路径.

关键词: 铂碳催化剂, Fe-N-C层, 轨道杂化, 酸性氧还原, 质子交换膜燃料电池

Abstract:

Pt/C catalysts are widely used for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) but suffer from limited stability. Herein, we demonstrate that the introduction of Fe-N-C layers onto the surface of Pt/C catalysts can significantly bolster both the ORR stability and activity of Pt/C in the harsh working environment of PEMFCs. Whilst Fe-N-C catalysts typically exhibit poor ORR activity and durability in acidic media, the obtained PtFe/C@Fe-N-C catalyst exhibits a very high peak power density of 2.03 W cm^-2 and an excellent mass activity (MA) of 0.75 A mg_Pt^-1 in a H₂-O₂ fuel cell, with only 2.7% decay after 30000 cycles, far superior to the Pt/C (0.176 A mg_Pt^-1 and 54.0% decay) and the U.S. Department of Energy 2025 targets. Experimental and density functional theory investigations unequivocally confirm that the Pt coated with optimized Fe-N-C layer contributes to a more delocalized electronic structure and stronger bonding between Pt and FeN_x via strong hybridization of 5d-3d/2p orbitals, resulting in the excellent activity and stability of the PtFe/C@Fe-N-C catalyst.

Key words: Pt/C catalysts, Fe-N-C layers, Orbital hybridization, Acid oxygen reduction reaction, Proton exchange membrane fuel cells

庄玉娟, 陈庆军, 林兴恩, 孟令伟, 胡富望, 余新涛, Geoffrey I. N. Waterhouse, 彭立山. 通过Fe-N-C层介导的5d-3d/2p耦合增强Pt/C催化剂在质子交换膜燃料电池中氧还原反应的稳定性研究[J]. 催化学报, 2026, 83: 308-318.

Yujuan Zhuang, Qingjun Chen, Xingen Lin, Lingwei Meng, Fuwang Hu, Xintao Yu, Geoffrey I. N. Waterhouse, Lishan Peng. Enhancing the stability of Pt/C catalysts for oxygen reduction reaction in PEMFCs via Fe-N-C-mediated 5d-3d/2p orbital hybridization[J]. Chinese Journal of Catalysis, 2026, 83: 308-318.

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图/表 5

Fig. 1. (a) Schematic representation of PtFe/C@Fe-N-C from a commercial Pt/C catalyst. (b) HAADF-STEM image and nanoparticle size distribution (inset) of PtFe/C@Fe-N-C. (c) XRD patterns for PtFe/C@Fe-N-C, PtFe/C, and Pt/C. (d) HRTEM image of PtFe/C@Fe-N-C. (e,f) HAADF-STEM image of PtFe/C@Fe-N-C showing the presence of PtFe nanoparticles covered by a thin Fe-N-C layer containing Fe single atoms. (g) HAADF-STEM micrographs along with EDS mapping images for PtFe/C@Fe-N-C.

Fig. 2. (a) Fe 2p XPS spectra with high resolution. (b) High-resolution Pt 4f XPS spectra for various PtFe/C@Fe-N-C catalysts with different Fe-N-C contents. (c) XPS binding energy gap for Fe2+ and Pt0 peaks relative to Fe-N-C/C and PtFe/C, respectively, with Fe-N-C layers of varying thicknesses. XANES spectra at Pt L3-edge (d) and Fe K-edge (e) for different catalysts. Corresponding FT-EXAFS spectra at Pt L3-edge (f) and Fe K-edge (g) in R-space. Difference XANES spectra at Pt L3-edge (h) and Fe K-edge (i). For better visualization, the intensity of the conventional XANES spectra was scaled by a factor of 0.2.

Fig. 3. (a) Relationship between the MA of PtFe/C@Fe-N-C catalysts with Fe-N-C layers of varying thicknesses and the XPS binding energy gap for Fe 2p (Fe2+) and Pt 4f (Pt0) peaks relative to Fe-N-C/C and PtFe/C, respectively. (b) ORR polarization curves for various catalysts collected in O2-saturated. (c) Mass activity and specific activity. (d) Polarization curves for PtFe/C@Fe-N-C, PtFe/C and Pt/C before and after undergoing different cycles. (e) Mass activity comparison of PtFe/C@Fe-N-C, PtFe/C and Pt/C before and after different cycles. (f) The change in average particle diameter for PtFe/C@Fe-N-C, PtFe/C and Pt/C after different cycles.

Fig. 4. Polarization curves and power density plots of PtFe/C@Fe-N-C and Pt/C under the conditions of H2-O2 (a) and H2-air (b). (c) H2-O2 fuel cell polarization curves and power density plots of PtFe/C@Fe-N-C prior to and post ADTs. (d) H2-O2 fuel cell polarization curves and power density plots of Pt/C prior to and post ADTs. MA (e) and cell voltage (f) at 0.8 A cm-2 for PtFe/C@Fe-N-C and Pt/C prior to and post ADTs. (g) Comparative analysis of BOL MA and MA retention post 30k ADT cycles versus recently reported advanced Pt-based catalysts. (h) The relative current of Pt/C and PtFe/C@Fe-N-C during the ADTs.

Fig. 5. (a) Charge density difference diagrams for Pt@C and PtFe@Fe-N-C, areas of charge depletion and accumulation are illustrated in cyan and yellow respectively. (b) The PDOS of PtFe@Fe-N-C. (c) Schematic diagram of the band structures of Pt@C, PtFe@Fe-N-C and Fe-N-C. (d) Gibbs free energy diagram (U = 1.23 V). (e) The dissolution energy of Fe and theoretical models for Fe-N-C and PtFe@Fe-N-C. The concentration of Pt (f) and Fe (g) collected in the electrolyte during ADTs. Color code: Pt (grey), Fe (purple), C (white), N (blue).

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通过Fe-N-C层介导的5d-3d/2p耦合增强Pt/C催化剂在质子交换膜燃料电池中氧还原反应的稳定性研究

Enhancing the stability of Pt/C catalysts for oxygen reduction reaction in PEMFCs via Fe-N-C-mediated 5d-3d/2p orbital hybridization

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