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Title: Highly active atomically dispersed CoN 4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy

Development of platinum group metal (PGM)-free catalysts for oxygen reduction reaction (ORR) is essential for affordable proton exchange membrane fuel cells. Herein, a new type of atomically dispersed Co doped carbon catalyst with a core–shell structure has been developed via a surfactant-assisted metal–organic framework approach. The cohesive interactions between the selected surfactant and the Co-doped zeolitic imidazolate framework (ZIF-8) nanocrystals lead to a unique confinement effect. During the thermal activation, this confinement effect suppressed the agglomeration of Co atomic sites and mitigated the collapse of internal microporous structures of ZIF-8. Among the studied surfactants, Pluronic F127 block copolymer led to the greatest performance gains with a doubling of the active site density relative to that of the surfactant-free catalyst. According to density functional theory calculations, unlike other Co catalysts, this new atomically dispersed Co–N–C@F127 catalyst is believed to contain substantial CoN 2+2 sites, which are active and thermodynamically favorable for the four-electron ORR pathway. The Co–N–C@F127 catalyst exhibits an unprecedented ORR activity with a half-wave potential (E 1/2) of 0.84 V (vs. RHE) as well as enhanced stability in the corrosive acidic media. It also demonstrated high initial performance with a power density of 0.87 W cm -2 along withmore » encouraging durability in H 2–O 2 fuel cells. The atomically dispersed Co site catalyst approaches that of the Fe–N–C catalyst and represents the highest reported PGM-free and Fe-free catalyst performance.« less
Authors:
ORCiD logo [1] ;  [2] ;  [3] ;  [4] ;  [4] ;  [5] ; ORCiD logo [6] ;  [7] ;  [7] ;  [1] ;  [1] ;  [7] ;  [3] ;  [8] ;  [5] ;  [4] ; ORCiD logo [1]
  1. State Univ. of New York (SUNY), Buffalo, NY (United States). Univ. at Buffalo, Dept. of Chemical and Biological Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  4. Carnegie Mellon Univ., Pittsburgh, PA (United States). Dept. of Mechanical Engineering
  5. Univ. of Pittsburgh, PA (United States). Dept. of Mechanical Engineering and Materials Science
  6. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering
  7. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  8. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Publication Date:
Report Number(s):
BNL-209357-2018-JAAM
Journal ID: ISSN 1754-5692; EESNBY
Grant/Contract Number:
SC0012704; EE0008076
Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Name: Energy & Environmental Science; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE
OSTI Identifier:
1480958
Alternate Identifier(s):
OSTI ID: 1480361

He, Yanghua, Hwang, Sooyeon, Cullen, David A., Uddin, M. Aman, Langhorst, Lisa, Li, Boyang, Karakalos, Stavros, Kropf, A. Jeremy, Wegener, Evan C., Sokolowski, Joshua, Chen, Mengjie, Myers, Debbie, Su, Dong, More, Karren L., Wang, Guofeng, Litster, Shawn, and Wu, Gang. Highly active atomically dispersed CoN4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy. United States: N. p., Web. doi:10.1039/C8EE02694G.
He, Yanghua, Hwang, Sooyeon, Cullen, David A., Uddin, M. Aman, Langhorst, Lisa, Li, Boyang, Karakalos, Stavros, Kropf, A. Jeremy, Wegener, Evan C., Sokolowski, Joshua, Chen, Mengjie, Myers, Debbie, Su, Dong, More, Karren L., Wang, Guofeng, Litster, Shawn, & Wu, Gang. Highly active atomically dispersed CoN4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy. United States. doi:10.1039/C8EE02694G.
He, Yanghua, Hwang, Sooyeon, Cullen, David A., Uddin, M. Aman, Langhorst, Lisa, Li, Boyang, Karakalos, Stavros, Kropf, A. Jeremy, Wegener, Evan C., Sokolowski, Joshua, Chen, Mengjie, Myers, Debbie, Su, Dong, More, Karren L., Wang, Guofeng, Litster, Shawn, and Wu, Gang. 2018. "Highly active atomically dispersed CoN4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy". United States. doi:10.1039/C8EE02694G.
@article{osti_1480958,
title = {Highly active atomically dispersed CoN4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy},
author = {He, Yanghua and Hwang, Sooyeon and Cullen, David A. and Uddin, M. Aman and Langhorst, Lisa and Li, Boyang and Karakalos, Stavros and Kropf, A. Jeremy and Wegener, Evan C. and Sokolowski, Joshua and Chen, Mengjie and Myers, Debbie and Su, Dong and More, Karren L. and Wang, Guofeng and Litster, Shawn and Wu, Gang},
abstractNote = {Development of platinum group metal (PGM)-free catalysts for oxygen reduction reaction (ORR) is essential for affordable proton exchange membrane fuel cells. Herein, a new type of atomically dispersed Co doped carbon catalyst with a core–shell structure has been developed via a surfactant-assisted metal–organic framework approach. The cohesive interactions between the selected surfactant and the Co-doped zeolitic imidazolate framework (ZIF-8) nanocrystals lead to a unique confinement effect. During the thermal activation, this confinement effect suppressed the agglomeration of Co atomic sites and mitigated the collapse of internal microporous structures of ZIF-8. Among the studied surfactants, Pluronic F127 block copolymer led to the greatest performance gains with a doubling of the active site density relative to that of the surfactant-free catalyst. According to density functional theory calculations, unlike other Co catalysts, this new atomically dispersed Co–N–C@F127 catalyst is believed to contain substantial CoN2+2 sites, which are active and thermodynamically favorable for the four-electron ORR pathway. The Co–N–C@F127 catalyst exhibits an unprecedented ORR activity with a half-wave potential (E1/2) of 0.84 V (vs. RHE) as well as enhanced stability in the corrosive acidic media. It also demonstrated high initial performance with a power density of 0.87 W cm-2 along with encouraging durability in H2–O2 fuel cells. The atomically dispersed Co site catalyst approaches that of the Fe–N–C catalyst and represents the highest reported PGM-free and Fe-free catalyst performance.},
doi = {10.1039/C8EE02694G},
journal = {Energy & Environmental Science},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {1}
}

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