Structural evolution of Pt-based oxygen reduction reaction electrocatalysts

doi:10.1016/S1872-2067(21)63896-2

Abstract

Abstract:

The commercialization of proton exchange membrane fuel cells (PEMFCs) could provide a cleaner energy society in the near future. However, the sluggish reaction kinetics and harsh conditions of the oxygen reduction reaction affect the durability and cost of PEMFCs. Most previous reports on Pt-based electrocatalyst designs have focused more on improving their activity; however, with the commercialization of PEMFCs, durability has received increasing attention. In-depth insight into the structural evolution of Pt-based electrocatalysts throughout their lifecycle can contribute to further optimization of their activity and durability. The development of in situ electron microscopy and other in situ techniques has promoted the elucidation of the evolution mechanism. This mini review highlights recent advances in the structural evolution of Pt-based electrocatalysts. The mechanisms are adequately discussed, and some methods to inhibit or exploit the structural evolution of the catalysts are also briefly reviewed.

Key words: Oxygen reduction reaction, Structural evolution, Pt-based electrocatalyst, Durability, In situ electron microscopy, characterizations

Jiaheng Peng, Peng Tao, Chengyi Song, Wen Shang, Tao Deng, Jianbo Wu. Structural evolution of Pt-based oxygen reduction reaction electrocatalysts[J]. Chinese Journal of Catalysis, 2022, 43(1): 47-58.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63896-2

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Figures/Tables 11

Fig. 1. (A) Pourbaix diagram of Pt(100); (B) CV spectra and corresponding dissolution amount of Pt(110), Pt(100), and Pt(111); (C) Graphical representation of the main reactions that occur at the Pt electrodes (pH = 1). Reprinted with permission from: (A) Ref. [7], copyright 2018, American Chemical Society and (B) Ref. [9], Copyright 2016, American Chemical Society.

Fig. 2. (A) CV spectra and in situ STM images of Pt(111); (B) Depiction of the surface roughing mechanism; (C) STM images of Pt(111) after different protocols. Reprinted with permission from: (A,B) Ref. [15], copyright 2017, American Chemical Society and (C) Ref. [14], Copyright 2018, Elsevier.

Fig. 3. (A) Sequential TEM images of the icosahedral and cubic Pt NPs; (B) Plots for the oxidative etching of the icosahedral Pt NPs at different stages of the reaction. (C) Analysis of the etching modes of the different sites on a cubic Pt NP. Reprinted with permission from Ref. [18], Copyright 2017, American Chemical Society.

Fig. 4. (A) TEM images; (B) Schematic of the etching process; (C) Strain map before etching; (D) Etching distance in the three directions; (E) Etching rates in the three directions. Reprinted with permission from Ref. [32], Copyright 2020, Elsevier.

Fig. 5. (A) Scheme of the synthesis of the Pt-Ir-Pd nanocages; (B) HAADF-STEM image and EDX maps of the Pt-Ir-Pd nanocage; (C) Scheme of the synthesis of porous Pt3Ni NWs; (D) TEM and HAADF-STEM images of the Pt3Ni6 NWs; (E) TEM and HAADF-STEM images of the porous treated Pt3Ni6 NWs. Reprinted with permission from: (A,B) Ref. [40], Copyright 2020, Wiley-VCH and (C-E) Ref. [42], Copyright 2017, Wiley-VCH.

Fig. 6. (A) Indirect nanoplasmonic sensing centroid shift vs. time in Ar at 453 K for Pt clusters with different size distributions; (B) Cluster area distribution before and after annealing. Reprinted with permission from Ref. [49], Copyright 2014, American Chemical Society.

Fig. 7. (A-C) HAADF-STEM images of PtM3/C; (D,E) STEM-EELS mapping of the PtCo3 and PtNi3 NPs; (F) Surface composition determined by XPS; (G,H) Structure models of (D) and (E); (I) Ni content and particle size of the PtNi3 NPs at 400 and 600 °C; (J) Scheme of the surface composition effect on coalescence. Reprinted with permission from ref. [56], Copyright 2020, American Chemical Society.

Fig. 8. (A) Scheme of the Pt NW formation process in the presence of H2; (B) TEM images of the growth process; (C) TEM images of oriented attachment growth along the Pt(100) facet. Reprinted with permission from Ref. [69], Copyright 2017, Wiley-VCH.

Fig. 9. (A,B) XANES spectra of the PtCo/C electrocatalyst at the Co K-edge before and after ADT using different potentials; (C-F) STEM images of an oxidized Pt3Co NP; (G,H) Bright-field STEM images of an oxidized Pt3Co NP. Reprinted with permission from: (A,B) Ref. [11], Copyright 2019, American Chemical Society; (C)-(H) Ref. [78], Copyright 2017, American Chemical Society.

Fig. 10. (A) Schematic diagram of the formation of phase-segregated octahedral PtNi NPs; (B-E) Elemental maps of the PtNi NPs during the synthesis process; (F-H) HAADF-STEM images of the phase-segregated hierarchical PtNi NPs and their derivatives produced by chemical etching; (I) EDX elemental maps of the octahedral skeletal Pt-based NPs. Reprinted with permission from Ref. [81], Copyright 2015, American Chemical Society.

Fig. 11. (A-D) HAADF-STEM images along the (100) surface; (E-H) HAADF-STEM images along the (110) surface; (I) Scheme of the evolution process of the Pt3Co NCs under LTDAP and DHTAP. Reprinted with permission from Ref. [88]. Copyright 2021, American Chemical Society.

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