Correlating the electrocatalytic stability of platinum monolayer catalysts with their structural evolution in the oxygen reduction reaction

Chen, Guangyu; Kuttiyiel, Kurian A.; Li, Meng; Su, Dong; Du, Lei; Du, Chunyu; Gao, Yunzhi; Fei, Weidong; Yin, Geping; Sasaki, Kotaro; Adzic, Radoslav R.

doi:10.1039/C8TA06686H

Title: Correlating the electrocatalytic stability of platinum monolayer catalysts with their structural evolution in the oxygen reduction reaction

Journal Article · 23 September 2018 · Journal of Materials Chemistry. A

DOI: https://doi.org/10.1039/C8TA06686H · OSTI ID:1488522

^[1]; Kuttiyiel, Kurian A. ^[2]; Li, Meng ^[2]; Su, Dong ^[2];

^[3];

^[3]; Gao, Yunzhi ^[3];

^[3];

^[2]; Adzic, Radoslav R. ^[2]

Harbin Institute of Technology (China); Brookhaven National Lab. (BNL), Upton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Harbin Institute of Technology (China)

Platinum monolayer (Pt_ML) core–shell electrocatalysts for the oxygen reduction reaction (ORR) have attracted great attention because of their exceptional activity and stability for promising practical applications in fuel cells. In this paper, we describe our in-depth investigation of the relationship between the ORR activity and structure of the Pt_ML/Pd/C catalyst during the stability test. By virtue of the rotating disk electrode technique, an accelerated degradation test with the potential window of 0.65 to 1.05 V was applied to the Pt_ML/Pd/C to interrogate its long-term reliability in the ORR, the change of its electrochemical surface area, and its surface composition and components. The Pt_ML/Pd/C catalyst displayed a volcano-like mass/dollar activity profile in the stability test up to 100k cycles. The overall loss of the activity was recorded to be as low as 17% of the initial value. The ORR activity increased in the initial 20k cycles because the freshly prepared Pt_ML did not entirely encompass the whole Pd core, but it was integrated to a full coverage with a more stable configuration during the potential cycling owing to its self-healing property. Then, the activity decreased at a much slower rate than the standard Pt/C because the Pd–Pt core–shell structure due to its structural self-retaining property remained intact and impeded the electrochemical Ostwald ripening of the entire particles. Changes in the morphology and configuration of Pt_ML were mapped by combining our experimental investigation with model analyses. Finally, the proposed self-healing and self-retaining mechanisms account for the structure-dependent stability in the ORR and play cornerstone roles in formulating ORR core–shell electrocatalysts.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0012704

OSTI ID:: 1488522

Report Number(s):: BNL-209808-2018-JAAM

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 42 Vol. 6; ISSN JMCAET; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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