Ultrafine L10 PtFeZn intermetallics via a two-step annealing process for oxygen reduction reaction: Decoupling alloying and ordering stages

doi:10.1016/S1872-2067(25)64805-4

Chinese Journal of Catalysis ›› 2025, Vol. 78: 324-335.DOI: 10.1016/S1872-2067(25)64805-4

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Ultrafine L1₀ PtFeZn intermetallics via a two-step annealing process for oxygen reduction reaction: Decoupling alloying and ordering stages

Yun-Fei Xia^a, Bo Liu^a, Zi-Yu Zhang^a, Zi-Gang Zhao^b, Pan Guo^a, Si Lin^a, Bing Liu^a, Yan Wang^a, Yun-Long Zhang^a^,^*(), Lei Zhao^a^,^*(), Li-Guang Wang^c^,^*(), Zhen-Bo Wang^a^,^*()

^aState Key Laboratory of Space Power-Sources, MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, Heilongjiang, China
^bKey Laboratory of Superlight Materials and Surface Technology of Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, Heilongjiang, China
^cCollege of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, Zhejiang, China

Received:2025-05-27 Accepted:2025-07-02 Online:2025-11-18 Published:2025-10-14
Contact: *E-mail: wangzhb@hit.edu.cn (Z.-B. Wang), 20220123@hit.edu.cn (Y.-L. Zhang), leizhao@hit.edu.cn (L. Zhao), wanglg@zju.edu.cn (L. G. Wang).
Supported by:
National Natural Science Foundation of China(U23A20573);National Natural Science Foundation of China(22409041);National Natural Science Foundation of China(22075062);Key Research and Development Program of Shandong Province(2022CXGC010305);Heilongjiang Touyan Team(HITTY-20190033);Natural Science Foundation of Heilongjiang Province of China(LH2024B013);Fundamental Research Funds for the Central Universities(FRFCU5710051922);Guangdong Basic and Applied Basic Research Foundation(2023B1515120022);Guangdong Basic and Applied Basic Research Foundation(2022B1515120001);Shenzhen Science and Technology Innovation Program(RCBS20231211090522040);Shenzhen Science and Technology Innovation Program(KJZD20240903095610014);Shenzhen Science and Technology Innovation Program(KJZD20240903095712017);High-Level Professional Team in Shenzhen(KQTD20210811090045006);Zhejiang Provincial Natural Science Foundation of China(LR24E020001);Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2023R01007)

Abstract

Abstract:

In this paper, we report the design of ultrafine ordered PtFeZn ternary intermetallics uniformly supported on ZIF-8-derived Zn,N-codoped graphitic carbon (ZnNC) via a green aqueous impregnation method followed by a two-step annealing protocol (H₂/Ar, 600 and 800 ℃) to circumvent the sintering issues imposed by conventional thermodynamics. Physical characterizations (X-ray diffraction, high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy) and theoretical calculations reveal that low-temperature annealing at 600 ℃ stabilizes sub-nano disordered PtFe alloys via the strong metal-support interactions (SMSI) between Zn in ZnNC and Pt precursors, while high-temperature treatment at 800 ℃ promotes Zn diffusion from the support into the alloy bulk and simultaneously triggers the disorder-to-order phase transition. The as-prepared ZnNC-15PtFeZn exhibits an initial mass activity of 0.769 mA/μg_Pt and retains 61.7% of its activity after 30000 cycles of accelerated stress testing (AST). Notably, when used as a cathode catalyst in MEA, ZnNC-15PtFeZn achieves superior power density (2.018 W/cm² under H₂-O₂) at half the Pt loading (0.05 mg/cm²) of state-of-the-art commercial Pt/C, highlighting its potential for low-Pt PEMFCs. Density functional theory confirms that Fe enhances ORR activity via ligand effects, while Zn strengthens Pt-Fe/Zn bonding (elevating vacancy formation energies), thereby improving structural stability. This mild, scalable aqueous impregnation strategy offers a general approach for synthesizing multi-component ordered alloys in electrocatalysis.

Key words: Oxygen reduction reaction, Zn-NC support, PtFeZn ternary intermetallic, Two-step annealing, Strong-metal support interaction

Yun-Fei Xia, Bo Liu, Zi-Yu Zhang, Zi-Gang Zhao, Pan Guo, Si Lin, Bing Liu, Yan Wang, Yun-Long Zhang, Lei Zhao, Li-Guang Wang, Zhen-Bo Wang. Ultrafine L1₀ PtFeZn intermetallics via a two-step annealing process for oxygen reduction reaction: Decoupling alloying and ordering stages[J]. Chinese Journal of Catalysis, 2025, 78: 324-335.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64805-4

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Figures/Tables 6

Table 1 hemical composition analysis (wt%) of carbon precursor and catalysts.

Sample	ZnNC		Comm-20PtC		XC72-15PtFe		ZnNC-15PtZn		ZnNC-15PtFeZn
Item	XPS ^a	ICP ^b	XPS	ICP	XPS	ICP	XPS	ICP	XPS	ICP
C	77.2	—	74.5	—	80.2	—	70.7	—	67.8	—
N	6.85	—	—	—	0.51	—	5.05	—	4.80	—
O	8.79	—	3.90	—	4.16	—	7.77	—	9.08	—
Zn	7.13	5.43	—	—	—	—	5.99	4.63	2.51	1.98
Fe	—	—	—	—	3.77	4.68	—	—	3.99	4.23
Pt	—	—	21.6	20.0	11.4	16.0	10.5	18.1	11.8	17.6

Fig. 1. (a) Formation mechanism of ZnNC-PtFeZn nanoparticles under the two-step annealing protocol. (b) XRD patterns of ZnNC-15PtFeZn and control samples. TEM images of ZnNC-15PtFeZn (c), XC72-15PtFe (e), and ZnNC-15PtZn (f). (d) SAED pattern of ZnNC-15PtFeZn.

Fig. 2. (a,b) HAADF-STEM images of ZnNC-15PtFeZn, and inset is the Z-contrast profile along the <110> axis of PtFeZn NP. (c-f) EDS mapping and line scanning of ZnNC-15PtFeZn. (g) Pt 4f XPS spectra of catalysts.

Fig. 3. XAS characterization of ZnNC-15PtFeZn and references. (a-c) L3-edge XANES spectra, FT-EXAFS, and WT analysis of Pt. (d-f) K-edge XANES spectra, FT-EXAFS, and WT analysis of Fe. (g,h) K-edge XANES spectra, FT-EXAFS, and wavelet transform analysis of Zn. (Pc in FePc and ZnPc is short for phthalocyanine)

Fig. 4. (a) CV curves in N2-saturated 0.1 mol/L HClO4. (b) ORR polarization in O2-saturated 0.1 mol/L HClO4. (c) Tafel slope. (d) Durability tests. (e) MEA performance. (f) Comparison of power density with those of recently reported catalysts.

Fig. 5. (a,b) Formation mechanism of L10 PtFeZn ternary alloy. (c) ORR reaction free energy diagrams of catalysts. (d) Possible ORR reaction pathways of ZnNC-15PtFeZn. (e) Vacancy formation energies of Pt, Fe, and Zn for catalysts.

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Ultrafine L1₀ PtFeZn intermetallics via a two-step annealing process for oxygen reduction reaction: Decoupling alloying and ordering stages

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