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Design strategies of Pd-based electrocatalysts for efficient oxygen reduction

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Abstract

Oxygen reduction reaction (ORR) occurs at the cathode of fuel cells and metal–air batteries, but usually suffers from sluggish kinetics. To solve this issue, efficient electrocatalysts are highly desired. Palladium (Pd)-based nanomaterials, as the most promising substitute of platinum (Pt), exhibit superior activity and stability in ORR electrocatalysis. The delicate regulation of the structure and/or composition shows great potential in improving the electrocatalytic ORR performance of Pd-based nanomaterials. In this review, we retrospect the recent advance of Pd-based ORR electrocatalysts, and analyses the relationship between nanostructure and catalytic performance. We start with the ORR mechanism and indicators of ORR performance in both alkaline and acidic media, followed by the synthetic methods for Pd-based nanoparticles. Then, we emphasize the design strategies of efficient Pd-based ORR catalysts from the perspective of composition, crystal phase, morphology, and support effects. Last but not least, we conclude with possible opportunities and outlook on Pd-based nanomaterials toward ORR.

Graphical abstract

摘要

氧还原反应(ORR)是燃料电池和金属空气电池的阴极反应，但通常动力学较为缓慢。为解决这个问题, 需要高效的电催化剂。作为最有希望的铂的替代材料，钯(Pd)基纳米材料在ORR电催化中表现出优异的活性和稳定性。 结构或组分的精准调控在改善Pd基纳米材料的电催化ORR性能方面显示出巨大的潜力。这篇综述介绍了Pd基ORR电催化剂的最新进展, 并分析了纳米结构与催化性能之间的关系。 本文首先讨论了ORR的反应机理及其在碱性和酸性介质中的性能指标，然后总结了Pd基纳米粒子的合成方法。接下来，从组分、晶相、形貌和载体的影响角度强调了高效Pd基ORR催化剂的设计策略。 最后，总结了Pd基纳米材料在ORR应用中可能面临的机遇和前景。

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Fig. 1
Fig. 2

Reproduced with permission from Ref. [35]. Copyright 2019, the Royal Society of Chemistry. b A volcano map of ORR activity as a function of oxygen binding energy. Redrawn with permission from Ref. [36]. Copyright 2004, American Chemical Society

Fig. 3

Reproduced with permission from Ref. [50]. Copyright 2018, the Royal Society of Chemistry. TEM images for c porous palladium nanostructures and d porous Au@Pd nanostructures. Reproduced with permission from Ref. [51]. Copyright 2013, Wiley–VCH. e, f SEM images of mesoporous Pd nanoparticles. Reproduced with permission from Ref. [52]. Copyright 2019, the Royal Society of Chemistry

Fig. 4

Reproduced with permission from Ref. [64]. Copyright 2015, American Chemical Society. e Schematic illustration for formation of mesoporous PdCu films with vertical mesochannels; f, g Top-view SEM images, h TEM image and i HAADF-STEM cross-sectional image of mesoporous Pd81Cu19 films. Reproduced with permission from Ref. [65]. Copyright 2018, American Chemical Society

Fig. 5

Reproduced with permission from Ref. [68]. Copyright 2013, Wiley–VCH. c, d SEM images of c Pd15Ce5Al80 alloy ribbon and d nanoporous PdCe nanocubes. Reproduced with permission from Ref. [69]. Copyright 2018, the Royal Society of Chemistry. e Illustration of electrochemical dealloying process of Pd/Ni or Pd/Mn; f STEM image and g corresponding elemental mapping images of Pd (red) and Ni (green) for PdNi/C before alloying; h STEM image and i corresponding elemental mapping images for PdNi/C after alloying. Reproduced with permission from Ref. [71]. Copyright 2020, American Chemical Society. j Illustration of synthesis of bimetallic CuPd alloy multipods by GRR from Ref. [79]. Copyright 2017, the Royal Society of Chemistry

Fig. 6

Reproduced with permission from Ref. [89]. Copyright 2019, American Chemical Society. d HAADF-STEM, e atomic-resolution aberration-corrected HAADF-STEM, and f STEM-EDX elemental mapping images of Pd3Pb ultrathin porous intermetallic nanosheets (UPINs); g polarization curves for Pd3Pb UPINs/C (green), Pd UNs/C (orange), Pt/C (red), and Pd/C (black) electrocatalysts toward ORR; h polarization curves of Pd3Pb UPINs/C before and after cycling test; i polarization curves of different electrocatalysts with addition of methanol. Reproduced with permission from Ref. [90]. Copyright 2021, Wiley–VCH

Fig. 7

Reproduced with permission from Ref. [29]. Copyright 2018, the Royal Society of Chemistry. c HAADF-STEM and d TEM images of porous Pd metallene; e ORR polarization curves of different catalysts. Reproduced with permission from Ref. [101]. Copyright 2021, Wiley–VCH. f HAADF-STEM image and g schematic diagram of Pd4Sn wavy nanowires; h ORR polarization curves for different electrocatalysts before and after 10,000 cycles of accelerated durability tests (ADTs). Reproduced with permission from Ref. [102]. Copyright 2019, American Chemical Society

Fig. 8

Reproduced with permission from Ref. [108]. Copyright 2021, American Chemical Society. b, c Monoclinic Pd5Bi2 and fcc Pd3Bi nanocrystals. Reproduced with permission from Ref. [109]. Copyright 2021, American Chemical Society. d fct-FePd/Pd nanoparticles. Reproduced with permission from Ref. [110]. Copyright 2015, American Chemical Society

Fig. 9

Reproduced with permission from Ref. [109]. Copyright 2021, American Chemical Society

Fig. 10

Reproduced with permission from Ref. [115]. Copyright 2015, American Chemical Society. c TEM image of AL-Pd/Mo2C embedded in octahedral carbon frameworks. d ORR polarization curves of different catalysts. Reproduced with permission from Ref. [119]. Copyright 2021, American Chemical Society. e TEM image of PdH0.706@Ni–B composites; f polarization curves of PdHx with different x value, Pt/C and PdH0.706@Ni–B/C catalysts. Reproduced with permission from Ref. [120]. Copyright 2017, Wiley–VCH

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (No. 52172058).

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  1. School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, China

    Chun-Jie Li, Chun-Xian Guo & Ru-Guang Ma

  2. School of Instrumentation Science and Opto-electronics Engineering, Beihang University, Beijing, 100083, China

    Guang-Cun Shan

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Li, CJ., Shan, GC., Guo, CX. et al. Design strategies of Pd-based electrocatalysts for efficient oxygen reduction. Rare Met. 42, 1778–1799 (2023). https://doi.org/10.1007/s12598-022-02234-4

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