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Title: Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells

Abstract

Platinum group metal (PGM)-free catalysts that are also Fe-free are highly desirable for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells, as they avoid possible Fenton reactions. Here we report an efficient ORR catalyst that consists of atomically dispersed nitrogen-coordinated single Mn sites on partially graphitic carbon (Mn-N-C). Evidence for the embedding of the atomically dispersed MnN4 moieties within the carbon surface-exposed basal planes was established by X-ray absorption spectroscopy and their dispersion was confirmed by aberration-corrected electron microscopy with atomic resolution. The Mn-N-C catalyst exhibited a half-wave potential of 0.80 V vs. RHE, approaching that of Fe-N-C catalysts, along with significantly enhanced stability in acidic media. The encouraging performance of the Mn-N-C catalyst as a PGM-free cathode was demonstrated in fuel cell tests. First-principles calculations further support the MnN4 sites as the origin of the ORR activity via a 4e- pathway in acidic media.

Authors:
 [1];  [2]; ORCiD logo [3];  [4];  [5];  [6];  [6]; ORCiD logo [7];  [5];  [2];  [8];  [8];  [9]; ORCiD logo [5]; ORCiD logo [4]; ORCiD logo [10];  [6]; ORCiD logo [11]; ORCiD logo [2]
  1. Harbin Inst. of Technology (China). MIIT Key Lab. of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering; Univ. at Buffalo, NY (United States). Dept. of Chemical and Biological Engineering
  2. Univ. at Buffalo, NY (United States). Dept. of Chemical and Biological Engineering
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  5. Oregon State Univ., Corvallis, OR (United States). School of Chemical Biological, and Environmental Engineering
  6. Univ. of Pittsburgh, PA (United States). Dept. of Mechanical Engineering and Materials Science
  7. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering
  8. Giner Inc., Newton, MA (United States)
  9. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  10. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  11. Harbin Inst. of Technology (China). MIIT Key Lab. of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Fuel Cell Technologies (FCTO)
OSTI Identifier:
1480959
Alternate Identifier(s):
OSTI ID: 1490583; OSTI ID: 1493892; OSTI ID: 1502572
Report Number(s):
BNL-209358-2018-JAAM
Journal ID: ISSN 2520-1158
Grant/Contract Number:  
AC05-00OR22725; SC0012704; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 1; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Li, Jiazhan, Chen, Mengjie, Cullen, David A., Hwang, Sooyeon, Wang, Maoyu, Li, Boyang, Liu, Kexi, Karakalos, Stavros, Lucero, Marcos, Zhang, Hanguang, Lei, Chao, Xu, Hui, Sterbinsky, George E., Feng, Zhenxing, Su, Dong, More, Karren L., Wang, Guofeng, Wang, Zhenbo, and Wu, Gang. Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells. United States: N. p., 2018. Web. doi:10.1038/s41929-018-0164-8.
Li, Jiazhan, Chen, Mengjie, Cullen, David A., Hwang, Sooyeon, Wang, Maoyu, Li, Boyang, Liu, Kexi, Karakalos, Stavros, Lucero, Marcos, Zhang, Hanguang, Lei, Chao, Xu, Hui, Sterbinsky, George E., Feng, Zhenxing, Su, Dong, More, Karren L., Wang, Guofeng, Wang, Zhenbo, & Wu, Gang. Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells. United States. doi:10.1038/s41929-018-0164-8.
Li, Jiazhan, Chen, Mengjie, Cullen, David A., Hwang, Sooyeon, Wang, Maoyu, Li, Boyang, Liu, Kexi, Karakalos, Stavros, Lucero, Marcos, Zhang, Hanguang, Lei, Chao, Xu, Hui, Sterbinsky, George E., Feng, Zhenxing, Su, Dong, More, Karren L., Wang, Guofeng, Wang, Zhenbo, and Wu, Gang. Mon . "Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells". United States. doi:10.1038/s41929-018-0164-8. https://www.osti.gov/servlets/purl/1480959.
@article{osti_1480959,
title = {Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells},
author = {Li, Jiazhan and Chen, Mengjie and Cullen, David A. and Hwang, Sooyeon and Wang, Maoyu and Li, Boyang and Liu, Kexi and Karakalos, Stavros and Lucero, Marcos and Zhang, Hanguang and Lei, Chao and Xu, Hui and Sterbinsky, George E. and Feng, Zhenxing and Su, Dong and More, Karren L. and Wang, Guofeng and Wang, Zhenbo and Wu, Gang},
abstractNote = {Platinum group metal (PGM)-free catalysts that are also Fe-free are highly desirable for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells, as they avoid possible Fenton reactions. Here we report an efficient ORR catalyst that consists of atomically dispersed nitrogen-coordinated single Mn sites on partially graphitic carbon (Mn-N-C). Evidence for the embedding of the atomically dispersed MnN4 moieties within the carbon surface-exposed basal planes was established by X-ray absorption spectroscopy and their dispersion was confirmed by aberration-corrected electron microscopy with atomic resolution. The Mn-N-C catalyst exhibited a half-wave potential of 0.80 V vs. RHE, approaching that of Fe-N-C catalysts, along with significantly enhanced stability in acidic media. The encouraging performance of the Mn-N-C catalyst as a PGM-free cathode was demonstrated in fuel cell tests. First-principles calculations further support the MnN4 sites as the origin of the ORR activity via a 4e- pathway in acidic media.},
doi = {10.1038/s41929-018-0164-8},
journal = {Nature Catalysis},
number = ,
volume = 1,
place = {United States},
year = {2018},
month = {10}
}

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Figures / Tables:

Fig. 1 Fig. 1: Schematic diagram of atomically dispersed MnN4 site catalyst synthesis. A two-step doping and adsorption approach can gradually increase the density of the atomically dispersed and nitrogen-coordinated MnN4 sites into the 3D carbon particles. In the first step, Mn-doped ZIF-8 precursors are carbonized and then leached with an acidmore » solution to prepare partially graphitized carbon host with optimal nitrogen doping and microporous structures. In the second step, additional Mn and N sources were adsorbed into the 3D carbon host followed by a thermal activation to generate increased density of MnN4 active sites.« less

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