Activating Nitrogen–doped Graphene Oxygen Reduction Electrocatalysts in Acidic Electrolytes using Hydrophobic Cavities and Proton–conductive Particles

Singh, Santosh K.; Takeyasu, Kotaro; Homma, Kaito; Ito, Shigeharu; Morinaga, Takashi; Endo, Yuto; Furukawa, Moeko; Mori, Toshiyuki; Ogasawara, Hirohito; Nakamura, Junji

doi:10.1002/anie.202212506

Title: Activating Nitrogen–doped Graphene Oxygen Reduction Electrocatalysts in Acidic Electrolytes using Hydrophobic Cavities and Proton–conductive Particles

Journal Article · Fri Oct 14 00:00:00 EDT 2022 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202212506· OSTI ID:1998894

Singh, Santosh K. ^[1];

^[2]; Homma, Kaito ^[2]; Ito, Shigeharu ^[3]; Morinaga, Takashi ^[3]; Endo, Yuto ^[4]; Furukawa, Moeko ^[4]; Mori, Toshiyuki ^[5]; Ogasawara, Hirohito ^[6]; Nakamura, Junji ^[7]

Univ. of Tsukuba (Japan); Shiv Nadar University, Greater Noida (India)
Univ. of Tsukuba (Japan)
Tsuruoka College, Yamagata (Japan)
University of Tsukuba (Japan)
National Institute for Materials Sciences (NIMS), Tsukuba (Japan)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
University of Tsukuba (Japan); Kyushu Univ., Fukuoka (Japan)

Although pyridinic-nitrogen (pyri-N) doped graphene is highly active for the oxygen reduction reaction (ORR) of fuel cells in alkaline media, the activity critically decreases under acidic conditions. Herein we report on how to prevent the deactivation based on the mechanistic understanding that O₂ + pyri–NH^⁺ + e^– → O_2,a + pyri–NH governs the ORR kinetics. First, we considered that the deactivation is due to the hydration of pyri-NH⁺, leading to a lower shift of the redox potential. Introducing the hydrophobic cavity prevented the hydration of pyri-NH⁺ but inhibited the proton transport. We then increased proton conductivity in the hydrophobic cavity by introducing SiO₂ particles coated with ionic liquid polymer/Nafion® which kept the high onset potentials with an increased current density even in acidic media.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); Japan Society for the Promotion of Science (JSPS) (KAKENHI); Kato Foundation for Promotion of Science

Grant/Contract Number:: AC02-76SF00515; 17F17345; 19K15356; 20H00316; KJ-3031

OSTI ID:: 1998894

Journal Information:: Angewandte Chemie (International Edition), Vol. 61, Issue 51; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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25 ENERGY STORAGE
fuel cell
N-doped graphene catalyst
oxygen reduction reaction

Title: Activating Nitrogen–doped Graphene Oxygen Reduction Electrocatalysts in Acidic Electrolytes using Hydrophobic Cavities and Proton–conductive Particles

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