4.8 Article

Electronic and Potential Synergistic Effects of Surface-Doped P-O Species on Uniform Pd Nanospheres: Breaking the Linear Scaling Relationship toward Electrochemical Oxygen Reduction

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 14, Issue 12, Pages 14146-14156

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c22935

Keywords

palladium; phosphorus; surface-doped nanostructure; nanosphere; synergistic effect; electrocatalyst; oxygen reduction reaction; linear scaling relationship

Funding

  1. National Natural Science Foundation of China [21975157]
  2. China Postdoctoral Science Foundation [2021M692062]
  3. Oceanic Interdisciplinary Program of Shanghai Jiao Tong University [SL2021ZD105]
  4. Center for HighPerformance Computing at Shanghai Jiao Tong University

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This study develops a low-cost and high-performance electrocatalyst for oxygen reduction reaction (ORR) and proposes a promising strategy for breaking the long-standing linear scaling relationship (LSR). The catalyst exhibits nearly ideal 4-electron ORR pathways under both alkaline and acidic conditions.
Developing efficient oxygen reduction reaction (ORR) electrocatalysts is critical to fuel cells and metal-oxygen batteries, but also greatly hindered by the limited Pt resources and the long-standing linear scaling relationship (LSR). In this study, similar to 6 nm and highly uniform Pd nanospheres (NSs) having surface-doped (SD) P-O species are synthesized and evenly anchored onto carbon blacks, which are further simply heat-treated (HT). Under alkaline conditions, Pd/P-SD-O NSs/C-HT exhibits respective 8.7 (4.3)- and 5.0 (5.5)-fold enhancements in noble-metal-mass- and area-specific activity (NM-MSA and ASA) compared with the commercial Pd/C (Pt/C). It also possesses an improved electrochemical stability. Besides, its acidic ASA and NM-MSA are 2.9 and 5.1 times those of the commercial Pd/C, respectively, and reach 65.4 and 51.5% of those of the commercial Pt/C. Moreover, it also shows nearly ideal 4-electron ORR pathways under both alkaline and acidic conditions. The detailed experimental and theoretical analyses reveal the following: (1) The electronic effect induced by the P-O species can downshift the surface d-band center to weaken the intermediate adsorptions, thus preserving more surface active sites. (2) More importantly, the potential hydrogen bond between the O atom in the P-O species and the H atom in the hydrogen-containing intermediates can in turn stabilize their adsorptions, thus breaking the ORR LSR toward more efficient ORRs and 4-electron pathways. This study develops a low-cost and high-performance ORR electrocatalyst and proposes a promising strategy for breaking the ORR LSR, which may be further applied in other electrocatalysis.

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