A novel core-shell nanostructure of Ti-Au nanocrystal with PtNi alloy skin: Enhancing the durability for oxygen reduction reaction

doi:10.1016/S1872-2067(23)64568-1

Abstract

Abstract:

The sluggish oxygen reduction reaction (ORR) at the cathode largely hinders the practical application of the proton-exchange membrane fuel cells (PEMFCs). Pt-based nanocrystals are the most effective electrocatalysts for the oxygen reduction reaction, however, suffer high cost, scarcity and unsatisfied durability. Herein, we report a new category of annealed multimetallic core-shell catalyst of gold core doped with titanium and platinum-nickel (PtNi) shell with Pt-rich surface as a highly active and robust electrocatalyst for ORR. The introduction of titanium can effectively stabilize the gold core, avoiding the outward migration of Au atoms and ensuring the exposure of Pt-Ni active sites. The experimental findings revealed that the annealed Ti-Au@PtNi NPs catalyst provides 19.26 and 9.84 times higher mass and specific activities than commercial Pt/C catalysts for the oxygen reduction reaction. Moreover, durability tests of annealed Ti-Au@PtNi NPs show no noticeable activity loss even after 20000 potential cycles between 0.6 and 1.0 V vs. RHE, demonstrating a promising catalyst for the oxygen reduction reaction.

Key words: Titanium doping, Pt-rich surface, Thermal annealing, Oxygen reduction reaction, Core-shell nanostructure

Giday Fisseha, Ya’nan Yu, Shaojie Lu, Yiping Hu, Yu Zhou, Qin Yue. A novel core-shell nanostructure of Ti-Au nanocrystal with PtNi alloy skin: Enhancing the durability for oxygen reduction reaction[J]. Chinese Journal of Catalysis, 2024, 56: 81-87.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64568-1

https://www.cjcatal.com/EN/Y2024/V56/I1/81

Figures/Tables 5

Fig. 1. Structural and compositional characterizations of Au@PtNi nanoparticles and Ti-Au@PtNi nanoparticles (Before and after annealing): TEM images of 4.56 nm Ti NPs (a), 5.20 nm Ti-Au NPs (b), 7.64 nm Ti-Au@PtNi NPs (c). (d) STEM-EDX images of Pt, Au and Ni of Au@PtNi/C NPs. (e) STEM-EDX images of Pt, Au and Ni of Au@PtNi/C NPs-400. (f) STEM-EDX images of Pt, Au, Ni and Ti of Ti-Au@PtNi/C NPs. (g) STEM-EDX images of Pt, Au, Ni and Ti of Ti-Au@PtNi/C NPs-400.

Fig. 2. (a) Comparison of XRD patterns of as-prepared Ti-Au@PtNi/C and Ti-Au@PtNi/C-400, (b) Comparison of XPS patterns of as-prepared Ti-Au@PtNi/C and Ti-Au@PtNi/C-400 (c) Pt 4f XPS spectra of as-prepared Ti-Au@PtNi/C and Ti-Au@PtNi/C-400, (d) Ni 2p XPS spectra of as-prepared Ti-Au@PtNi/C and Ti-Au@PtNi/C-400, (e) Ti 2p XPS spectra of as-prepared Ti-Au@PtNi/C and Ti-Au@PtNi/C-400, (f) Au 4f XPS spectra of as-prepared Ti-Au@PtNi/C and Ti-Au@PtNi/C-400.

Fig. 3. Electrochemical performance of catalysts. (a) CV curves of Pt/C, Au@PtNi/C, Ti-Au@PtNi/C and Ti-Au@PtNi/C-400. (b) LSV curves of Pt/C, Au@PtNi/C, Ti-Au@PtNi/C and Ti-Au@PtNi/C-400. (c) Histogram of ECSA of Pt/C, Au@PtNi/C, as-prepared Ti-Au@PtNi/C and Ti-Au@PtNi/C-400. (d) Summary of specific activities and mass activities for the ORR @0.9 V vs. RHE with 1600 r min?1 at a sweep rate of 20 mV s?1 of Pt/C, Au@PtNi/C, as-prepared Ti-Au@PtNi/C and Ti-Au@PtNi/C-400.

Fig. 4. Durability performance of catalysts. (a) ORR polarization curves before and after different potential cycles for Ti-Au@PtNi/C. (b) Specific and mass activity evolutions for various potential cycles. (c) ORR polarization curves before and after different potential cycles for Ti-Au@PtNi/C-400. (d) Specific and mass activity evolutions for various potential cycles.

Fig. 5. Fuel-cell performance of various catalysts. Air-H2 fuel cell polarization plots with the Ti-Au@PtNi/C-400, Ti-Au@PtNi/C and Pt/C as cathode catalysts. Test conditions: 80 °C, 100% relative humidity, atmospheric backpressure. Air and H2 flow rates were fixed at 0.2 and 0.1 L min?1.

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