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Title: 3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: a balance between graphitization and hierarchical porosity

Abstract

Carbon supports used in oxygen-reduction cathode catalysts for proton exchange membrane fuel cells (PEMFCs) are vulnerable to corrosion under harsh operating conditions, leading to poor performance durability. To address this issue, we have developed highly stable porous graphitic carbon (PGC) produced through pyrolysis of a 3D polymer hydrogel in combination with Mn. The resulting PGC features multilayer carbon sheets assembled in porous and flower-like morphologies. In situ high-temperature electron microscopy was employed to dynamically monitor the carbonization process up to 1100 °C, suggesting that the 3D polymer hydrogel provides high porosity at multiple scales, and that Mn catalyzes the graphitization process more effectively than other metals. Compared to conventional carbon supports such as Vulcan, Ketjenblack, and graphitized carbon, PGC provides an improved balance between high graphitization and hierarchical porosity, which is favorable for uniform Pt nanoparticle dispersion and enhanced corrosion resistance. As a result, Pt supported on PGC exhibits remarkably enhanced stability. In addition to thorough testing in aqueous electrolytes, we also conducted fuel cell testing using durability protocols recommended by the U.S. Department of Energy (DOE). After 5000 voltage cycles from 1.0 to 1.5 V, the Pt/PGC catalyst only lost 9 mV at a current density of 1.5 Amore » cm-2, dramatically exceeding the DOE support durability target (<30 mV), and surpassing commercial Pt/C catalysts. Along with the enhanced carbon corrosion resistance of the PGC support, the enhanced catalyst–support interactions are beneficial for stability improvement, likely due to nitrogen doping into carbon, which was further elucidated through X-ray absorption spectroscopy and density functional theory (DFT) calculations. Finally, the high stability and activity of PGC-based Pt catalysts are attributed to the combination of high graphitization degree, favorable surface area and porosity, and nitrogen doping, which effectively stabilize highly dispersed Pt nanoparticles.« less

Authors:
 [1];  [2];  [2]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [3];  [1]; ORCiD logo [1];  [4];  [6];  [6];  [7]; ORCiD logo [4];  [2]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. State Univ. of New York, Buffalo, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Oregon State Univ., Corvallis, OR (United States)
  5. Univ. of South Carolina, Columbia, SC (United States)
  6. Univ. of Pittsburgh, PA (United States)
  7. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (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), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1581280
Alternate Identifier(s):
OSTI ID: 1543417; OSTI ID: 1545900; OSTI ID: 1573498
Report Number(s):
LA-UR-19-27316; BNL-211914-2019-JAAM
Journal ID: ISSN 1754-5692; EESNBY
Grant/Contract Number:  
89233218CNA000001; AC02-06CH11357; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 12; Journal Issue: 9; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE

Citation Formats

Qiao, Zhi, Hwang, Sooyeon, Li, Xing, Wang, Chenyu, Samarakoon, Widitha, Karakalos, Stavros, Li, Dongguo, Chen, Mengjie, He, Yanghua, Wang, Maoyu, Liu, Zhenyu, Wang, Guofeng, Zhou, Hua, Feng, Zhenxing, Su, Dong, Spendelow, Jacob Schatz, and Wu, Gang. 3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: a balance between graphitization and hierarchical porosity. United States: N. p., 2019. Web. doi:10.1039/C9EE01899A.
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Qiao, Zhi, Hwang, Sooyeon, Li, Xing, Wang, Chenyu, Samarakoon, Widitha, Karakalos, Stavros, Li, Dongguo, Chen, Mengjie, He, Yanghua, Wang, Maoyu, Liu, Zhenyu, Wang, Guofeng, Zhou, Hua, Feng, Zhenxing, Su, Dong, Spendelow, Jacob Schatz, & Wu, Gang. 3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: a balance between graphitization and hierarchical porosity. United States. https://doi.org/10.1039/C9EE01899A
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Qiao, Zhi, Hwang, Sooyeon, Li, Xing, Wang, Chenyu, Samarakoon, Widitha, Karakalos, Stavros, Li, Dongguo, Chen, Mengjie, He, Yanghua, Wang, Maoyu, Liu, Zhenyu, Wang, Guofeng, Zhou, Hua, Feng, Zhenxing, Su, Dong, Spendelow, Jacob Schatz, and Wu, Gang. Mon . "3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: a balance between graphitization and hierarchical porosity". United States. https://doi.org/10.1039/C9EE01899A. https://www.osti.gov/servlets/purl/1581280.
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@article{osti_1581280,
title = {3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: a balance between graphitization and hierarchical porosity},
author = {Qiao, Zhi and Hwang, Sooyeon and Li, Xing and Wang, Chenyu and Samarakoon, Widitha and Karakalos, Stavros and Li, Dongguo and Chen, Mengjie and He, Yanghua and Wang, Maoyu and Liu, Zhenyu and Wang, Guofeng and Zhou, Hua and Feng, Zhenxing and Su, Dong and Spendelow, Jacob Schatz and Wu, Gang},
abstractNote = {Carbon supports used in oxygen-reduction cathode catalysts for proton exchange membrane fuel cells (PEMFCs) are vulnerable to corrosion under harsh operating conditions, leading to poor performance durability. To address this issue, we have developed highly stable porous graphitic carbon (PGC) produced through pyrolysis of a 3D polymer hydrogel in combination with Mn. The resulting PGC features multilayer carbon sheets assembled in porous and flower-like morphologies. In situ high-temperature electron microscopy was employed to dynamically monitor the carbonization process up to 1100 °C, suggesting that the 3D polymer hydrogel provides high porosity at multiple scales, and that Mn catalyzes the graphitization process more effectively than other metals. Compared to conventional carbon supports such as Vulcan, Ketjenblack, and graphitized carbon, PGC provides an improved balance between high graphitization and hierarchical porosity, which is favorable for uniform Pt nanoparticle dispersion and enhanced corrosion resistance. As a result, Pt supported on PGC exhibits remarkably enhanced stability. In addition to thorough testing in aqueous electrolytes, we also conducted fuel cell testing using durability protocols recommended by the U.S. Department of Energy (DOE). After 5000 voltage cycles from 1.0 to 1.5 V, the Pt/PGC catalyst only lost 9 mV at a current density of 1.5 A cm-2, dramatically exceeding the DOE support durability target (<30 mV), and surpassing commercial Pt/C catalysts. Along with the enhanced carbon corrosion resistance of the PGC support, the enhanced catalyst–support interactions are beneficial for stability improvement, likely due to nitrogen doping into carbon, which was further elucidated through X-ray absorption spectroscopy and density functional theory (DFT) calculations. Finally, the high stability and activity of PGC-based Pt catalysts are attributed to the combination of high graphitization degree, favorable surface area and porosity, and nitrogen doping, which effectively stabilize highly dispersed Pt nanoparticles.},
doi = {10.1039/C9EE01899A},
journal = {Energy & Environmental Science},
number = 9,
volume = 12,
place = {United States},
year = {2019},
month = {7}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/C9EE01899A
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Cited by: 18 works
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Figures / Tables:

Figure 1 Figure 1: (a) Synthesis scheme for porous graphitic carbons (PGCs) derived from polymer hydrogel; TEM, HRTEM and STEM images of (b) Mn-PANI-PGC and (c) Mn-PANI-PPy-PGC at different magnifications.
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    Engineering Local Coordination Environments of Atomically Dispersed and Heteroatom‐Coordinated Single Metal Site Electrocatalysts for Clean Energy‐Conversion
    journal, November 2019

    • Zhu, Yuanzhi; Sokolowski, Joshua; Song, Xiancheng
    • Advanced Energy Materials, Vol. 10, Issue 11
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