Hierarchically skeletal multi-layered Pt-Ni nanocrystals for highly efficient oxygen reduction and methanol oxidation reactions

doi:10.1016/S1872-2067(20)63680-4

Abstract

Abstract:

Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) in fuel cells. Maximizing the utilization of Pt based materials by modulating their morphologies to expose more active sites is a fundamental objective for the practical application of fuel cells. Herein, we report a new class of hierarchically skeletal Pt-Ni nanocrystals (HSNs) with a multi-layered structure, prepared by an inorganic acid-induced solvothermal method. The addition of H₂SO₄ to the synthetic protocol provides a critical trigger for the successful growth of Pt-Ni nanocrystals with the desired structure. The Pt-Ni HSNs synthesized by this method exhibit enhanced mass activity of 1.25 A mg_pt^-1 at 0.9 V (versus the reversible hydrogen electrode) towards ORR in 0.1-M HClO₄, which is superior to that of Pt-Ni multi-branched nanocrystals obtained by the same method in the absence of inorganic acid; it is additionally 8.9-fold higher than that of the commercial Pt/C catalyst. Meanwhile, it displays enhanced stability, with only 21.6% mass activity loss after 10,000 cycles (0.6-1.0 V) for ORR. Furthermore, the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for MOR. The superb activity of the Pt-Ni HSNs for ORR and MOR is fully attributed to an extensively exposed electrochemical surface area and high intrinsic activity, induced by strain effects, provided by the unique hierarchically skeletal alloy structure. The novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.

Key words: Hierarchically skeletal Pt-Ni nanocrystals, Self-assembly, Solvent thermal method, Oxygen reduction reaction, Methanol oxidation reaction, Fuel cells, Activity

Shibo Li, Zhi Qun Tian, Yang Liu, Zheng Jang, Syed Waqar Hasan, Xingfa Chen, Panagiotis Tsiakaras, Pei Kang Shen. Hierarchically skeletal multi-layered Pt-Ni nanocrystals for highly efficient oxygen reduction and methanol oxidation reactions[J]. Chinese Journal of Catalysis, 2021, 42(4): 648-657.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63680-4

https://www.cjcatal.com/EN/Y2021/V42/I4/648

Figures/Tables 8

Fig. 1. Pt-Ni bimetallic nanocomposites synthesized with the inclusion of H2SO4 in the first step: (a) SEM image, (b) low-resolution TEM images and line profile analysis, (c,d) high-magnification TEM image and (e) HAADF-STEM image with elemental mapping of a single particle. Hierarchically skeletal Pt-Ni nanocrystals (HSNs) after acid-leaching treatment: (f,g) STEM image, (h,i) high-resolution TEM images and (g) the HAADF-STEM image with EDS mapping images of a single Pt-Ni HSN.

Fig. 2. Multi-branched Pt-Ni catalyst synthesized without H2SO4: (a,b) the HAADF-STEM image of the (MBs) and (c) EDS mapping images. (d) Bright-field TEM image of an individual Pt-Ni MB; (e) the corresponding local HR-TEM image. The inset shows the corresponding FFT pattern. (f) The EDS spectra and atomic compositions of Pt-Ni MBs.

Fig. 3. HAADF-STEM images of Pt-Ni HSNs obtained at 5 (a), 8 (b), 12 (c), 16 (d), and 20 (e) h and after the chemical etching process (f). The insets depict high magnification images of the corresponding individual Pt-Ni nanostructure.

Scheme 1. The growth mechanism of Pt-Ni HSNs.

Fig. 4. (a) XRD patterns of Pt-Ni HSNs, Pt-Ni MBs, and commercial Pt/C; The corresponding XPS spectra of Pt 4f (b) and Ni 2p (c).

Fig. 5. Electrochemical properties of the Pt-Ni HSNs/C catalyst, Pt-Ni MBs and commercial Pt/C catalyst toward ORR. (a) CV curves in N2-saturated electrolyte at 50 mV s-1; (b) LSV recorded at 10 mV s-1 and 1600 rpm; (c) Mass activity comparison at 0.9 V versus RHE; (d) Normalized mass activity; (e) ORR polarization curves of the Pt-Ni HSNs and the TKK-Pt/C before and after scanning 10,000 cycles in 0.1 M HClO4 aqueous solution; (f) Performance comparison with Pt/C.

Fig. 6. (a) Tafel plots for the Pt-Ni HSNs/C catalyst, Pt-Ni MBs and commercial Pt/C catalyst; (b) the curve for the RRDE test; (c) the curve of electron transfer number of the Pt-Ni HSNs/C catalyst.

Fig. 7. Electrochemical performances of the as-prepared Pt-Ni HSNs, Pt-Ni MBs and commercial Pt/C catalysts toward MOR. (a) CV curves in 0.5-M H2SO4 + 1.0-M CH3OH aqueous solution; (b) Mass activity of the three catalysts at the peak potential; (c) CO stripping voltammograms of the three catalysts in 0.5 M H2SO4.

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