Cooperative Atomically Dispersed Fe–N4 and Sn–Nx Moieties for Durable and More Active Oxygen Electroreduction in Fuel Cells

Xia, Fan; Li, Bomin; An, Bowen; Zachman, Michael J.; Xie, Xiaohong; Liu, Yiqi; Xu, Shicheng; Saha, Sulay; Wu, Qin; Gao, Siyuan; Abdul Razak, Iddrisu B.; Brown, Dennis E.; Ramani, Vijay; Wang, Rongyue; Marks, Tobin J.; Shao, Yuyan; Cheng, Yingwen

doi:10.1021/jacs.4c11121

Cooperative Atomically Dispersed Fe–N₄ and Sn–N_x Moieties for Durable and More Active Oxygen Electroreduction in Fuel Cells

Journal Article · Mon Dec 02 00:00:00 EST 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c11121· OSTI ID:2479314

^[1]; ^[2]; ^[2]; ^[3]; Xie, Xiaohong ^[4]; Liu, Yiqi ^[5]; Xu, Shicheng ^[6]; ^[7]; ^[8]; ^[9]; Abdul Razak, Iddrisu B. ^[10]; Brown, Dennis E. ^[10]; ^[7]; Wang, Rongyue ^[11]; ^[5]; Shao, Yuyan ^[4]; ^[1]

University of Tennessee, Knoxville, TN (United States); Northern Illinois University, DeKalb, IL (United States)
University of Tennessee, Knoxville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Northwestern University, Evanston, IL (United States)
Jinetics Inc., Santa Clara, CA (United States)
Washington University in St. Louis, MO (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Northern Illinois University, DeKalb, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Northern Illinois University, DeKalb, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

One grand challenge for deploying porous carbons with embedded metal–nitrogen–carbon (M–N–C) moieties as platinum group metal (PGM)-free electrocatalysts in proton-exchange membrane fuel cells is their fast degradation and inferior activity. Here, we report the modulation of the local environment at Fe–N₄ sites via the application of atomic Sn–N_x sites for simultaneously improved durability and activity. We discovered that Sn–N_x sites not only promote the formation of the more stable D2 FeN₄C₁₀ sites but also invoke a unique D3 SnN_x–Fe^IIN₄ site that is characterized by having atomically dispersed bridged Sn–N_x and Fe–N₄. This new D3 site exhibits significantly improved stability against demetalation and several times higher turnover frequency for the oxygen reduction reaction (ORR) due to the shift of the reaction pathway from a single-site associative mechanism to a dual-site dissociative mechanism with the adjacent Sn site facilitating a lower overpotential cleavage of the O–O bond. This mechanism bypasses the formation of the otherwise inevitable intermediate that is responsible for demetalation, where two hydroxyl intermediates bind to one Fe site. Lastly, a mesoporous Fe/Sn-PNC catalyst exhibits a positively shifted ORR half-wave potential and more than 50% lower peroxide formation. This, in combination with the stable D3 site and enriched D2 Fe sites, significantly enhanced the catalyst’s durability as demonstrated in membrane electrode assemblies using complementary accelerated durability testing protocols.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Northwestern University, Evanston, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); University of Tennessee, Knoxville, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; AC05-76RL01830; SC0012704; SC0023266; SC0024448

OSTI ID:: 2479314

Alternate ID(s):: OSTI ID: 2499434
OSTI ID: 2560283
OSTI ID: 2573835
OSTI ID: 2573257

Report Number(s):: BNL--226438-2024-JAAM; PNNL-SA--204466

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 49 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
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Cooperative Atomically Dispersed Fe–N4 and Sn–Nx Moieties for Durable and More Active Oxygen Electroreduction in Fuel Cells

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Cooperative Atomically Dispersed Fe–N₄ and Sn–N_x Moieties for Durable and More Active Oxygen Electroreduction in Fuel Cells