High index surface-exposed and composition-graded PtCu3@Pt3Cu@Pt nanodendrites for high-performance oxygen reduction

doi:10.1016/S1872-2067(20)63735-4

Abstract

Abstract:

Alloying and nanostructuring are two strategies used to facilitate the efficient electrocatalysis of the oxygen reduction reaction (ORR) by Pt, where the high index surfaces (HISs) of Pt exhibit superior activity for ORR. Here, we report the fabrication of PtCu₃ nanodendrites possessing rich spiny branches exposing n(111) × (110) HISs. The dendrites were formed through an etching-modulated seeding and growing strategy. Specifically, an oxidative atmosphere was initially applied to form the concaved nanocubes of the Pt-Cu seeds, which was then switched to an inert atmosphere to promote an explosive growth of dendrites. Separately, the oxidative or inert atmosphere failed to produce this hyperbranched structure. Electrochemical dealloying of the PtCu₃ nanodendrites produced Pt₃Cu shells with Pt-rich surfaces where HIS-exposed dendrite structures were maintained. The resulting PtCu₃@Pt₃Cu@Pt nanodendrites in 0.1 M HClO₄ exhibited excellent mass and area specific activities for ORR, which were 14 and 24 times higher than that of commercial Pt/C, respectively. DFT calculations revealed that Cu alloying and HISs both contributed to the significantly enhanced activity of Pt, and that the oxygen binding energy on the step sites of HISs on the PtCu₃@Pt₃Cu@Pt nanodendrites approached the optimal value to achieve a near peak-top ORR activity.

Key words: Oxygen reduction, Pt-Cu alloy, High-index-surfaces, Nanodendrites, Shape control

Yuxiang Liao, Jun Li, Shiming Zhang, Shengli Chen. High index surface-exposed and composition-graded PtCu₃@Pt₃Cu@Pt nanodendrites for high-performance oxygen reduction[J]. Chinese Journal of Catalysis, 2021, 42(7): 1108-1116.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63735-4

https://www.cjcatal.com/EN/Y2021/V42/I7/1108

Figures/Tables 6

Scheme 1. Schematic of the formation of Pt-Cu nanocrystals.

Fig. 1. TEM characterization results: (a,b) five-fold twinned nanocrystals formed under an Ar atmosphere in the initial 5 min of the seeding stage and (c) multipods grown under an Ar atmosphere for another 25 min; (d,e) concave nanocubes formed under air in the initial 5 min of the seeding stage and (f) large concave nanocubes grown under air for another 25 min; (g-i) hyperbranched nanodendrites (inset of g shows the corresponding SAED pattern) grown from the concave nanocubes by switching to the Ar atmosphere for 25 min after the seeding stage (i) and its inset show the magnified images of a typical spiny branch and the exposed HISs in the square-marked region which are detailed in text; (j,k) HAADF-STEM, EDX mapping images and EDX line scanning profiles of an individual hyperbranched nanodendrite.

Fig. 2. (a,b) TEM and HRTEM image of the dealloyed PtCu3 NDs; (c-f) EDX mapping results of the dealloyed PtCu3 NDs.

Fig. 3. Electrochemical properties of the three dealloyed Pt-Cu NCs/C and Pt/C in 0.1 M HClO4 solution. (a) ORR polarization curves; (b) cyclic voltammograms; (c) mass-specific activities; (d) area-specific activities at 0.9 V (vs. RHE).

Fig. 4. Models and calculated values of -AEO (with respect to that on Pt(111)) for PtCu3@Pt3Cu@Pt(111), PtCu3@Pt3Cu@Pt(332), and pure Pt (111).

Fig. 5. Electrochemical durability of the PtCu3@Pt3Cu@Pt hyperbranched nanodendrites and Pt/C catalysts: ORR polarization curves (a), mass-specific activity (b), and CV curves of PtCu3@Pt3Cu@Pt (c) and Pt/C (d) before and after 5000 cycles. The Pt loading of PtCu3@Pt3Cu@Pt and Pt/C is 7.5 μgPt cm-2 60 μgPt cm-2, respectively.

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High index surface-exposed and composition-graded PtCu₃@Pt₃Cu@Pt nanodendrites for high-performance oxygen reduction

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