Atomic Scaled Depth Correlation to the Oxygen Reduction Reaction Performance of Single Atom Ni Alloy to the NiO2 Supported Pd Nanocrystal

Haolin Li; Sheng Dai; Yawei Wu; Qi Dong; Jianjun Chen; Hsin-Yi Tiffany Chen; Alice Hu; Jyh-Pin Chou; Tsan-Yao Chen

doi:10.1002/advs.202207109

Atomic Scaled Depth Correlation to the Oxygen Reduction Reaction Performance of Single Atom Ni Alloy to the NiO₂ Supported Pd Nanocrystal

Adv Sci (Weinh). 2023 Apr;10(11):e2207109. doi: 10.1002/advs.202207109. Epub 2023 Feb 8.

Authors

Haolin Li^{1

2

3}, Sheng Dai⁴, Yawei Wu³, Qi Dong⁵, Jianjun Chen¹, Hsin-Yi Tiffany Chen², Alice Hu^{3

6}, Jyh-Pin Chou⁷, Tsan-Yao Chen^{2

8

9}

Affiliations

¹ School of Materials Science and Engineering, Zhejiang Sci-Tech University, Hangzhou, 310018, China.
² Department of Engineering and System Science, National Tsing Hua University, Hsinchu, 300044, Taiwan.
³ Department of Mechanical Engineering, City University of Hong Kong, Hong Kong SAR, 999077, China.
⁴ School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200234, China.
⁵ Department of Electrical Engineering, Tsinghua University, Beijing, 100084, China.
⁶ Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong SAR, 999077, China.
⁷ Department of Physics, National Changhua University of Education, Changhua, 50007, Taiwan.
⁸ Hierarchical Green-Energy Materials (Hi-GEM) Research Centre, National Cheng Kung University, Tainan, 70101, Taiwan.
⁹ Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei, 10617, Taiwan.

Abstract

This study demonstrates the intercalation of single-atom Ni (Ni^SA ) substantially reduces the reaction activity of Ni oxide supported Pd nanoparticle (NiO₂ /Pd) in the oxygen reduction reaction (ORR). The results indicate the transition states kinetically consolidate the adsorption energy for the chemisorbed O and OH species on the ORR activity. Notably, the NiO₂ /Ni¹ /Pd performs the optimum ORR behavior with the lowest barrier of 0.49 eV and moderate second-step barrier of 0.30 eV consequently confirming its utmost ORR performance. Through the stepwise cross-level demonstrations, a structure-E_ads -ΔE correspondence for the proposed NiO₂ /Niⁿ /Pd systems is established. Most importantly, such a correspondence reveals that the electronic structure of heterogeneous catalysts can be significantly differed by the segregation of atomic clusters in different dimensions and locations. Besides, the doping-depth effect exploration of the Ni^SA in the NiO₂ /Pd structure intrinsically elucidates that the Ni atom doping in the subsurface induces the most fruitful Ni^SA /Pd^ML synergy combining the electronic and strain effects to optimize the ORR, whereas this desired synergy diminishes at high Pd coverages. Overall, the results not only rationalize the variation in the redox properties but most importantly provides a precision evaluation of the process window for optimizing the configuration and composition of bimetallic catalysts in practical experiments.

Keywords: DFT calculations; bimetallic catalysts; fuel cell; oxygen reduction reaction.

Abstract

Grants and funding