PtCu nano-dendrites with enhanced stability in proton exchange membrane fuel cells

doi:10.1016/S1872-2067(25)64712-7

Abstract

Abstract:

The rigorous operating condition of proton exchange membrane fuel cells (PEMFCs) poses a substantial hurdle for the long-term stability of Pt-based alloy catalysts; thus, the development of Pt-alloy catalysts with unique morphologies is crucial for enhancing the stability of PEMFCs. In this study, we synthesized a novel PtCu nano-dendrite (PtCuND) catalyst through a facile, one-step solvothermal process. The sub-nanometer particles and nanopores within this catalyst facilitate enhanced mass transport. In PEM single-cell tests, the PtCuND catalyst displays high activity and robust stability, achieving a mass activity of 0.65 A mg_Pt^-1. Notably, after accelerated durability tests, the mass activity and the voltage at 0.8 A cm^-2 of PtCuND exhibits only minimal decreases of 18.5% and 9 mV, respectively. The combined experimental results and theoretical calculations conclusively illustrate the optimized adsorption of oxygen species and the impact of compressive strain on the catalyst surface. The enhanced durability can be attributed to the maintained nano-dendritic morphology and the strengthened interaction within the Pt-Cu bonds. This work not only enhances the stability of PEMFCs but also provides a robust foundation for the future scaling up of catalyst production, paving the way for widespread application in sustainable energy systems.

Key words: PtCu nano-dendrites, Oxygen reduction reaction, Enhanced stability, Proton-exchange-membrane fuel cell, Sustainable energy system

Chenhao Li, Hao Wang, Weiwei Wang, Shuo Bai, Zhongbin Gong, Qinqin Sang, Yuqing Zhang, Feng Huo, Yanrong Liu. PtCu nano-dendrites with enhanced stability in proton exchange membrane fuel cells[J]. Chinese Journal of Catalysis, 2025, 73: 322-333.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64712-7

https://www.cjcatal.com/EN/Y2025/V73/I6/322

Figures/Tables 6

Fig. 1. (a) Depiction of the synthesis route for PtCu nano-dendrites. TEM images (b), HAADF-STEM images (c), SAED images (d), atomic-level HAADF-STEM images (e), elemental mappings (f), and line-profile (g) of Pt77Cu23ND.

Fig. 2. XRD patterns (a), enlarged view of the Pt (111) crystal plane (b), Pt 4f XPS spectra (c) of the PtCuNDs. XANES and EXAFS at the Pt L3-edge (d,e) and the Cu K-edge (f,g), and wavelet transform analysis at the Pt L3-edge (h) of the samples.

Fig. 3. The ORR performance. CV curves (a), LSV curves (b), Tafel slopes (c), MA (d), and SA (e) of PtCuNDs and Pt/C. (f) Electron transfer numbers (n) and H2O2 yield (H2O2%) of Pt77Cu23ND and Pt/C. (g-i) LSV curves and MA changes of Pt77Cu23ND and Pt/C before and after ADT.

Fig. 4. Stability mechanism analysis. TEM image and corresponding particle size distribution (inset) (a), HAADF-STEM image (b), elemental mappings (c) of Pt77Cu23ND after ADT. TEM images and corresponding particle size distributions (inset) of Pt/C before (d) and after (e) ADT. (f) Structural evolution scheme of Pt/C during ADT. (g) Pt retention after ADT. (h) XPS analysis before and after ADT. (i) Calculated vacancy formation energy of surface Pt and Cu atoms (grey and yellow spheres represent Pt and Cu, respectively).

Fig. 5. Catalytic mechanism analysis. (a) Models of PtCuNDs and pure Pt (side view). (b) PDOS of pure Pt and PtCuNDs. (c) Relationships between the MA and oxygen adsorption energies of PtCuNDs and Pt. (d) ORR reaction pathways for Pt77Cu23ND. (e) Gibbs free energy diagram of the ORR on Pt (111) and Pt77Cu23ND (111) at 1.23 V. (f,g) Charge density difference calculations of the adsorption of OH* on Pt (111) and Pt77Cu23ND (111) (grey, yellow, red and white spheres represent Pt, Cu, O and H, respectively).

Fig. 6. PEM single-cell performance. (a) H2-O2 fuel cell polarization curves at low current densities of Pt77Cu23ND, Pt/C, and PtND. (b) H2-air fuel cell polarization curves and power density curves of Pt77Cu23ND and Pt/C. (c) H2-O2 fuel cell polarization curves of Pt77Cu23ND and Pt/C before (BOL) and after (EOL) ADT. (d) H2-air fuel cell polarization curves and power density curves before and after ADT of Pt77Cu23ND and Pt/C. (e) MA of Pt77Cu23ND and Pt/C before and after ADT. (f) Voltage at 0.8 A cm-2 for Pt77Cu23ND and Pt/C before and after ADT. (g) Comparison of the voltage drop at 0.8 A cm-2 in H2-air and MA loss for recently reported catalysts after ADT.

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