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 »
- Authors:
-
- State Univ. of New York, Buffalo, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Oregon State Univ., Corvallis, OR (United States)
- Univ. of South Carolina, Columbia, SC (United States)
- Univ. of Pittsburgh, PA (United States)
- 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.
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
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.
@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}
}
Web of Science
Figures / Tables:

Works referenced in this record:
Preparation and enhanced capacitance of core–shell polypyrrole/polyaniline composite electrode for supercapacitors
journal, January 2008
- Mi, Hongyu; Zhang, Xiaogang; Ye, Xiangguo
- Journal of Power Sources, Vol. 176, Issue 1
Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects
journal, July 2007
- Ferrari, Andrea C.
- Solid State Communications, Vol. 143, Issue 1-2, p. 47-57
Embedding Pt Nanocrystals in N-Doped Porous Carbon/Carbon Nanotubes toward Highly Stable Electrocatalysts for the Oxygen Reduction Reaction
journal, March 2015
- Guo, Lin; Jiang, Wen-Jie; Zhang, Yun
- ACS Catalysis, Vol. 5, Issue 5
Interaction between Pt nanoparticles and carbon nanotubes – An X-ray absorption near edge structures (XANES) study
journal, April 2007
- Zhou, Jigang; Zhou, Xingtai; Sun, Xuhui
- Chemical Physics Letters, Vol. 437, Issue 4-6
Size-controlled large-diameter and few-walled carbon nanotube catalysts for oxygen reduction
journal, January 2015
- Wang, Xianliang; Li, Qing; Pan, Hengyu
- Nanoscale, Vol. 7, Issue 47
Raman spectroscopic characterization of some commercially available carbon black materials
journal, January 1995
- Jawhari, T.; Roid, A.; Casado, J.
- Carbon, Vol. 33, Issue 11
Recent advances in activity and durability enhancement of Pt/C catalytic cathode in PEMFC
journal, October 2007
- Yu, Xingwen; Ye, Siyu
- Journal of Power Sources, Vol. 172, Issue 1
Understanding and approaches for the durability issues of Pt-based catalysts for PEM fuel cell
journal, September 2007
- Shao, Yuyan; Yin, Geping; Gao, Yunzhi
- Journal of Power Sources, Vol. 171, Issue 2, p. 558-566
Catalytic graphitization of carbons by various metals
journal, January 1979
- Ōya, Asao; Ōtani, Sugio
- Carbon, Vol. 17, Issue 2
Investigation of Further Improvement of Platinum Catalyst Durability with Highly Graphitized Carbon Nanotubes Support
journal, April 2008
- Wang, Jiajun; Yin, Geping; Shao, Yuyan
- The Journal of Physical Chemistry C, Vol. 112, Issue 15
Modeling the Structure and Composition of Nanoparticles by Extended X-Ray Absorption Fine-Structure Spectroscopy
journal, July 2011
- Frenkel, Anatoly I.; Yevick, Aaron; Cooper, Chana
- Annual Review of Analytical Chemistry, Vol. 4, Issue 1
Carbon nanofibers supported Pt–Ru electrocatalysts for direct methanol fuel cells
journal, January 2006
- Guo, Junsong; Sun, Gongquan; Wang, Qi
- Carbon, Vol. 44, Issue 1
High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt
journal, April 2011
- Wu, G.; More, K. L.; Johnston, C. M.
- Science, Vol. 332, Issue 6028, p. 443-447
Performance Durability of Polyaniline-derived Non-precious Cathode Catalysts
journal, January 2009
- Wu, Gang; Artyushkova, Kateryna; Ferrandon, Magali
- ECS Transactions, Vol. 25, Issue 1, p. 1299-1311
A review of the stability and durability of non-precious metal catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells
journal, July 2015
- Banham, Dustin; Ye, Siyu; Pei, Katie
- Journal of Power Sources, Vol. 285
Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction
journal, January 2018
- Weng, Zhe; Wu, Yueshen; Wang, Maoyu
- Nature Communications, Vol. 9, Issue 1
Novel catalyst support materials for PEM fuel cells: current status and future prospects
journal, January 2009
- Shao, Yuyan; Liu, Jun; Wang, Yong
- Journal of Materials Chemistry, Vol. 19, Issue 1, p. 46-59
Biomass-Derived Sponge-like Carbonaceous Hydrogels and Aerogels for Supercapacitors
journal, April 2013
- Wu, Xi-Lin; Wen, Tao; Guo, Hong-Li
- ACS Nano, Vol. 7, Issue 4
Observation of Raman band shifting with excitation wavelength for carbons and graphites
journal, July 1981
- Vidano, R. P.; Fischbach, D. B.; Willis, L. J.
- Solid State Communications, Vol. 39, Issue 2
Nitrogen-Doped Graphene-Rich Catalysts Derived from Heteroatom Polymers for Oxygen Reduction in Nonaqueous Lithium–O 2 Battery Cathodes
journal, October 2012
- Wu, Gang; Mack, Nathan H.; Gao, Wei
- ACS Nano, Vol. 6, Issue 11
Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells
journal, October 2018
- Li, Jiazhan; Chen, Mengjie; Cullen, David A.
- Nature Catalysis, Vol. 1, Issue 12
First principles study of doped carbon supports for enhanced platinum catalysts
journal, January 2010
- Holme, Timothy; Zhou, Yingke; Pasquarelli, Robert
- Physical Chemistry Chemical Physics, Vol. 12, Issue 32
Synthesis–structure–performance correlation for polyaniline–Me–C non-precious metal cathode catalysts for oxygen reduction in fuel cells
journal, January 2011
- Wu, Gang; Johnston, Christina M.; Mack, Nathan H.
- Journal of Materials Chemistry, Vol. 21, Issue 30
Electric Field Effect Tuning of Electron-Phonon Coupling in Graphene
journal, April 2007
- Yan, Jun; Zhang, Yuanbo; Kim, Philip
- Physical Review Letters, Vol. 98, Issue 16
Catalytic Graphitization of Carbon Aerogels by Transition Metals
journal, May 2000
- Maldonado-Hódar, F. J.; Moreno-Castilla, C.; Rivera-Utrilla, J.
- Langmuir, Vol. 16, Issue 9
Metal-Organic Framework-Derived Bamboo-like Nitrogen-Doped Graphene Tubes as an Active Matrix for Hybrid Oxygen-Reduction Electrocatalysts
journal, November 2014
- Li, Qing; Pan, Hengyu; Higgins, Drew
- Small, Vol. 11, Issue 12
Synthesis of nitrogen-doped onion-like carbon and its use in carbon-based CoFe binary non-precious-metal catalysts for oxygen-reduction
journal, October 2011
- Wu, Gang; Nelson, Mark; Ma, Shuguo
- Carbon, Vol. 49, Issue 12
Pt alloy nanoparticles decorated on large-size nitrogen-doped graphene tubes for highly stable oxygen-reduction catalysts
journal, January 2018
- Chen, Mengjie; Hwang, Sooyeon; Li, Jiazhan
- Nanoscale, Vol. 10, Issue 36
3D polymer hydrogel for high-performance atomic iron-rich catalysts for oxygen reduction in acidic media
journal, December 2017
- Qiao, Zhi; Zhang, Hanguang; Karakalos, Stavros
- Applied Catalysis B: Environmental, Vol. 219
Electrosynthesis and capacitive performance of polyaniline-polypyrrole composite
journal, November 2010
- Zhang, Ai-Qin; Zhang, Yong; Wang, Li-Zhen
- Polymer Composites, Vol. 32, Issue 1
Synthesis of iron-dispersed carbons by pressure pyrolysis of divinylbenzene-vinylferrocene copolymer
journal, September 1983
- Hirano, Shin-Ichi; Yogo, Toshinobu; Suzuki, Hirohiko
- Journal of Materials Science, Vol. 18, Issue 9
Dynamic traction of lattice-confined platinum atoms into mesoporous carbon matrix for hydrogen evolution reaction
journal, January 2018
- Zhang, Huabin; An, Pengfei; Zhou, Wei
- Science Advances, Vol. 4, Issue 1
Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon
journal, November 2017
- Gupta, Shiva; Zhao, Shuai; Wang, Xiao Xia
- ACS Catalysis, Vol. 7, Issue 12
3D Nitrogen-Doped Graphene Aerogel-Supported Fe 3 O 4 Nanoparticles as Efficient Electrocatalysts for the Oxygen Reduction Reaction
journal, May 2012
- Wu, Zhong-Shuai; Yang, Shubin; Sun, Yi
- Journal of the American Chemical Society, Vol. 134, Issue 22
Quantitative structural and textural assessment of laminar pyrocarbons through Raman spectroscopy, electron diffraction and few other techniques
journal, August 2006
- Vallerot, Jean-Marie; Bourrat, Xavier; Mouchon, Arnaud
- Carbon, Vol. 44, Issue 9
Preparation and characterization of Pt supported on graphene with enhanced electrocatalytic activity in fuel cell
journal, February 2011
- Xin, Yuchen; Liu, Jian-guo; Zhou, Yong
- Journal of Power Sources, Vol. 196, Issue 3
Multicomponent electrocatalyst with ultralow Pt loading and high hydrogen evolution activity
journal, July 2018
- Tiwari, Jitendra N.; Sultan, Siraj; Myung, Chang Woo
- Nature Energy, Vol. 3, Issue 9
Synthesis and analysis of thin conducting pyrolytic carbon films
journal, March 2012
- McEvoy, Niall; Peltekis, Nikolaos; Kumar, Shishir
- Carbon, Vol. 50, Issue 3
Self-Assembled Fe-N-Doped Carbon Nanotube Aerogels with Single-Atom Catalyst Feature as High-Efficiency Oxygen Reduction Electrocatalysts
journal, February 2017
- Zhu, Chengzhou; Fu, Shaofang; Song, Junhua
- Small, Vol. 13, Issue 15
A highly active, stable and synergistic Pt nanoparticles/Mo2C nanotube catalyst for methanol electro-oxidation
journal, January 2015
- Zhang, Kai; Yang, Wei; Ma, Chao
- NPG Asia Materials, Vol. 7, Issue 1
Influence of Nitrogen Doping on Oxygen Reduction Electrocatalysis at Carbon Nanofiber Electrodes
journal, March 2005
- Maldonado, Stephen; Stevenson, Keith J.
- The Journal of Physical Chemistry B, Vol. 109, Issue 10, p. 4707-4716
Is Ammonium Peroxydisulfate Indispensable for Preparation of Aniline-Derived Iron-Nitrogen-Carbon Electrocatalysts?
journal, August 2016
- Xie, Nan-Hong; Yan, Xiang-Hui; Xu, Bo-Qing
- ChemSusChem, Vol. 9, Issue 17
Raman scattering of laser-deposited amorphous carbon
journal, April 1993
- Bacsa, W. S.; Lannin, J. S.; Pappas, D. L.
- Physical Review B, Vol. 47, Issue 16
Evidence of a Unique Electron Donor−Acceptor Property for Platinum Nanoparticles as Studied by XPS
journal, May 2006
- Qiu, Limei; Liu, Fen; Zhao, Liangzhong
- Langmuir, Vol. 22, Issue 10
Catalytic Nanoarchitectures--the Importance of Nothing and the Unimportance of Periodicity
journal, March 2003
- Rolison, D. R.
- Science, Vol. 299, Issue 5613
Breakdown of the adiabatic Born–Oppenheimer approximation in graphene
journal, February 2007
- Pisana, Simone; Lazzeri, Michele; Casiraghi, Cinzia
- Nature Materials, Vol. 6, Issue 3
First-Principles Predictions of Structure–Function Relationships of Graphene-Supported Platinum Nanoclusters
journal, May 2016
- Shi, Hongbo; Auerbach, Scott M.; Ramasubramaniam, Ashwin
- The Journal of Physical Chemistry C, Vol. 120, Issue 22
Raman spectrum of modified PAN-based carbon fibers during graphitization
journal, January 1996
- Ko, Tse-Hao
- Journal of Applied Polymer Science, Vol. 59, Issue 4
Carbon-Supported Pt-Based Alloy Electrocatalysts for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells: Particle Size, Shape, and Composition Manipulation and Their Impact to Activity
journal, April 2015
- Wang, Yan-Jie; Zhao, Nana; Fang, Baizeng
- Chemical Reviews, Vol. 115, Issue 9
Ex Situ and In Situ Stability Studies of PEMFC Catalysts
journal, January 2005
- Stevens, D. A.; Hicks, M. T.; Haugen, G. M.
- Journal of The Electrochemical Society, Vol. 152, Issue 12
Remarkable support effect of SWNTs in Pt catalyst for methanol electrooxidation
journal, December 2005
- Wu, Gang; Chen, Yong-Sheng; Xu, Bo-Qing
- Electrochemistry Communications, Vol. 7, Issue 12
Nitrogen-doped carbon nanostructures and their composites as catalytic materials for proton exchange membrane fuel cell
journal, February 2008
- Shao, Yuyan; Sui, Jiehe; Yin, Geping
- Applied Catalysis B: Environmental, Vol. 79, Issue 1, p. 89-99
Purification and structural annealing of multiwalled carbon nanotubes at graphitization temperatures
journal, September 2001
- Andrews, R.; Jacques, D.; Qian, D.
- Carbon, Vol. 39, Issue 11
Self-crosslinked polyaniline hydrogel electrodes for electrochemical energy storage
journal, October 2015
- Guo, Haitao; He, Weina; Lu, Yun
- Carbon, Vol. 92
Enhancement of Pt and Pt-alloy fuel cell catalyst activity and durability via nitrogen-modified carbon supports
journal, January 2010
- Zhou, Yingke; Neyerlin, Kenneth; Olson, Tim S.
- Energy & Environmental Science, Vol. 3, Issue 10
Phosphate-Tolerant Oxygen Reduction Catalysts
journal, August 2014
- Li, Qing; Wu, Gang; Cullen, David A.
- ACS Catalysis, Vol. 4, Issue 9
Facile Synthesis of Polyaniline-Polypyrrole Nanofibers for Application in Chemical Deposition of Metal Nanoparticles
journal, July 2008
- Xu, Ping; Han, Xijiang; Wang, Chao
- Macromolecular Rapid Communications, Vol. 29, Issue 16
Hydrogel-derived non-precious electrocatalysts for efficient oxygen reduction
journal, July 2015
- You, Bo; Yin, Peiqun; Zhang, Junli
- Scientific Reports, Vol. 5, Issue 1
Recent advances in activity and durability enhancement of Pt/C catalytic cathode in PEMFC
journal, October 2007
- Yu, Xingwen; Ye, Siyu
- Journal of Power Sources, Vol. 172, Issue 1
Quantitative structural and textural assessment of laminar pyrocarbons through Raman spectroscopy, electron diffraction and few other techniques
text, January 2007
- Vallerot, Jean-Marie; Bourrat, Xavier; Mouchon, Arnaud
- arXiv
Works referencing / citing this record:
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
Figures / Tables found in this record: