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

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

doi:10.1039/C9EE01899A

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

Journal Article · Mon Jul 15 00:00:00 EDT 2019 · Energy & Environmental Science

DOI:https://doi.org/10.1039/C9EE01899A· OSTI ID:1581280

Qiao, Zhi ^[1]; Hwang, Sooyeon ^[2]; Li, Xing ^[2];

^[3]; Samarakoon, Widitha ^[4];

^[5];

^[3]; Chen, Mengjie ^[1];

^[1]; Wang, Maoyu ^[4]; Liu, Zhenyu ^[6]; Wang, Guofeng ^[6]; Zhou, Hua ^[7];

^[4]; Su, Dong ^[2];

^[3];

^[1]

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)

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.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: 89233218CNA000001; AC02-06CH11357; SC0012704

OSTI ID:: 1581280

Alternate ID(s):: OSTI ID: 1543417; OSTI ID: 1545900; OSTI ID: 1573498

Report Number(s):: LA-UR-19-27316; BNL-211914-2019-JAAM; EESNBY

Journal Information:: Energy & Environmental Science, Vol. 12, Issue 9; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 183 works

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References (60)

Preparation and enhanced capacitance of core–shell polypyrrole/polyaniline composite electrode for supercapacitors Mi, Hongyu; Zhang, Xiaogang; Ye, Xiangguo Journal of Power Sources, Vol. 176, Issue 1 https://doi.org/10.1016/j.jpowsour.2007.10.070	journal	January 2008
Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects Ferrari, Andrea C. Solid State Communications, Vol. 143, Issue 1-2, p. 47-57 https://doi.org/10.1016/j.ssc.2007.03.052	journal	July 2007
Embedding Pt Nanocrystals in N-Doped Porous Carbon/Carbon Nanotubes toward Highly Stable Electrocatalysts for the Oxygen Reduction Reaction Guo, Lin; Jiang, Wen-Jie; Zhang, Yun ACS Catalysis, Vol. 5, Issue 5 https://doi.org/10.1021/acscatal.5b00117	journal	March 2015
Interaction between Pt nanoparticles and carbon nanotubes – An X-ray absorption near edge structures (XANES) study Zhou, Jigang; Zhou, Xingtai; Sun, Xuhui Chemical Physics Letters, Vol. 437, Issue 4-6 https://doi.org/10.1016/j.cplett.2007.02.026	journal	April 2007
Size-controlled large-diameter and few-walled carbon nanotube catalysts for oxygen reduction Wang, Xianliang; Li, Qing; Pan, Hengyu Nanoscale, Vol. 7, Issue 47 https://doi.org/10.1039/C5NR05864C	journal	January 2015
Raman spectroscopic characterization of some commercially available carbon black materials Jawhari, T.; Roid, A.; Casado, J. Carbon, Vol. 33, Issue 11 https://doi.org/10.1016/0008-6223(95)00117-V	journal	January 1995
Recent advances in activity and durability enhancement of Pt/C catalytic cathode in PEMFC Yu, Xingwen; Ye, Siyu Journal of Power Sources, Vol. 172, Issue 1 https://doi.org/10.1016/j.jpowsour.2007.07.048	journal	October 2007
Understanding and approaches for the durability issues of Pt-based catalysts for PEM fuel cell Shao, Yuyan; Yin, Geping; Gao, Yunzhi Journal of Power Sources, Vol. 171, Issue 2, p. 558-566 https://doi.org/10.1016/j.jpowsour.2007.07.004	journal	September 2007
Catalytic graphitization of carbons by various metals Ōya, Asao; Ōtani, Sugio Carbon, Vol. 17, Issue 2 https://doi.org/10.1016/0008-6223(79)90020-4	journal	January 1979
Investigation of Further Improvement of Platinum Catalyst Durability with Highly Graphitized Carbon Nanotubes Support Wang, Jiajun; Yin, Geping; Shao, Yuyan The Journal of Physical Chemistry C, Vol. 112, Issue 15 https://doi.org/10.1021/jp800186p	journal	April 2008
Modeling the Structure and Composition of Nanoparticles by Extended X-Ray Absorption Fine-Structure Spectroscopy Frenkel, Anatoly I.; Yevick, Aaron; Cooper, Chana Annual Review of Analytical Chemistry, Vol. 4, Issue 1 https://doi.org/10.1146/annurev-anchem-061010-113906	journal	July 2011
Carbon nanofibers supported Pt–Ru electrocatalysts for direct methanol fuel cells Guo, Junsong; Sun, Gongquan; Wang, Qi Carbon, Vol. 44, Issue 1 https://doi.org/10.1016/j.carbon.2005.06.047	journal	January 2006
High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt Wu, G.; More, K. L.; Johnston, C. M. Science, Vol. 332, Issue 6028, p. 443-447 https://doi.org/10.1126/science.1200832	journal	April 2011
Performance Durability of Polyaniline-derived Non-precious Cathode Catalysts Wu, Gang; Artyushkova, Kateryna; Ferrandon, Magali ECS Transactions, Vol. 25, Issue 1, p. 1299-1311 https://doi.org/10.1149/1.3210685	journal	January 2009
A review of the stability and durability of non-precious metal catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells Banham, Dustin; Ye, Siyu; Pei, Katie Journal of Power Sources, Vol. 285 https://doi.org/10.1016/j.jpowsour.2015.03.047	journal	July 2015
Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction Weng, Zhe; Wu, Yueshen; Wang, Maoyu Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-02819-7	journal	January 2018
Novel catalyst support materials for PEM fuel cells: current status and future prospects Shao, Yuyan; Liu, Jun; Wang, Yong Journal of Materials Chemistry, Vol. 19, Issue 1, p. 46-59 https://doi.org/10.1039/B808370C	journal	January 2009
Biomass-Derived Sponge-like Carbonaceous Hydrogels and Aerogels for Supercapacitors Wu, Xi-Lin; Wen, Tao; Guo, Hong-Li ACS Nano, Vol. 7, Issue 4 https://doi.org/10.1021/nn400566d	journal	April 2013
Observation of Raman band shifting with excitation wavelength for carbons and graphites Vidano, R. P.; Fischbach, D. B.; Willis, L. J. Solid State Communications, Vol. 39, Issue 2 https://doi.org/10.1016/0038-1098(81)90686-4	journal	July 1981
Nitrogen-Doped Graphene-Rich Catalysts Derived from Heteroatom Polymers for Oxygen Reduction in Nonaqueous Lithium–O ₂ Battery Cathodes Wu, Gang; Mack, Nathan H.; Gao, Wei ACS Nano, Vol. 6, Issue 11 https://doi.org/10.1021/nn303275d	journal	October 2012
Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells Li, Jiazhan; Chen, Mengjie; Cullen, David A. Nature Catalysis, Vol. 1, Issue 12 https://doi.org/10.1038/s41929-018-0164-8	journal	October 2018
First principles study of doped carbon supports for enhanced platinum catalysts Holme, Timothy; Zhou, Yingke; Pasquarelli, Robert Physical Chemistry Chemical Physics, Vol. 12, Issue 32 https://doi.org/10.1039/b927263a	journal	January 2010
Synthesis–structure–performance correlation for polyaniline–Me–C non-precious metal cathode catalysts for oxygen reduction in fuel cells Wu, Gang; Johnston, Christina M.; Mack, Nathan H. Journal of Materials Chemistry, Vol. 21, Issue 30 https://doi.org/10.1039/c0jm03613g	journal	January 2011
Electric Field Effect Tuning of Electron-Phonon Coupling in Graphene Yan, Jun; Zhang, Yuanbo; Kim, Philip Physical Review Letters, Vol. 98, Issue 16 https://doi.org/10.1103/PhysRevLett.98.166802	journal	April 2007
Catalytic Graphitization of Carbon Aerogels by Transition Metals Maldonado-Hódar, F. J.; Moreno-Castilla, C.; Rivera-Utrilla, J. Langmuir, Vol. 16, Issue 9 https://doi.org/10.1021/la991080r	journal	May 2000
Metal-Organic Framework-Derived Bamboo-like Nitrogen-Doped Graphene Tubes as an Active Matrix for Hybrid Oxygen-Reduction Electrocatalysts Li, Qing; Pan, Hengyu; Higgins, Drew Small, Vol. 11, Issue 12 https://doi.org/10.1002/smll.201402069	journal	November 2014
Synthesis of nitrogen-doped onion-like carbon and its use in carbon-based CoFe binary non-precious-metal catalysts for oxygen-reduction Wu, Gang; Nelson, Mark; Ma, Shuguo Carbon, Vol. 49, Issue 12 https://doi.org/10.1016/j.carbon.2011.05.036	journal	October 2011
Pt alloy nanoparticles decorated on large-size nitrogen-doped graphene tubes for highly stable oxygen-reduction catalysts Chen, Mengjie; Hwang, Sooyeon; Li, Jiazhan Nanoscale, Vol. 10, Issue 36 https://doi.org/10.1039/C8NR05888A	journal	January 2018
3D polymer hydrogel for high-performance atomic iron-rich catalysts for oxygen reduction in acidic media Qiao, Zhi; Zhang, Hanguang; Karakalos, Stavros Applied Catalysis B: Environmental, Vol. 219 https://doi.org/10.1016/j.apcatb.2017.08.008	journal	December 2017
Electrosynthesis and capacitive performance of polyaniline-polypyrrole composite Zhang, Ai-Qin; Zhang, Yong; Wang, Li-Zhen Polymer Composites, Vol. 32, Issue 1 https://doi.org/10.1002/pc.20983	journal	November 2010
Synthesis of iron-dispersed carbons by pressure pyrolysis of divinylbenzene-vinylferrocene copolymer Hirano, Shin-Ichi; Yogo, Toshinobu; Suzuki, Hirohiko Journal of Materials Science, Vol. 18, Issue 9 https://doi.org/10.1007/BF00547598	journal	September 1983
Dynamic traction of lattice-confined platinum atoms into mesoporous carbon matrix for hydrogen evolution reaction Zhang, Huabin; An, Pengfei; Zhou, Wei Science Advances, Vol. 4, Issue 1 https://doi.org/10.1126/sciadv.aao6657	journal	January 2018
Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon Gupta, Shiva; Zhao, Shuai; Wang, Xiao Xia ACS Catalysis, Vol. 7, Issue 12 https://doi.org/10.1021/acscatal.7b02949	journal	November 2017
3D Nitrogen-Doped Graphene Aerogel-Supported Fe ₃ O ₄ Nanoparticles as Efficient Electrocatalysts for the Oxygen Reduction Reaction Wu, Zhong-Shuai; Yang, Shubin; Sun, Yi Journal of the American Chemical Society, Vol. 134, Issue 22 https://doi.org/10.1021/ja3030565	journal	May 2012
Quantitative structural and textural assessment of laminar pyrocarbons through Raman spectroscopy, electron diffraction and few other techniques Vallerot, Jean-Marie; Bourrat, Xavier; Mouchon, Arnaud Carbon, Vol. 44, Issue 9 https://doi.org/10.1016/j.carbon.2005.12.029	journal	August 2006
Preparation and characterization of Pt supported on graphene with enhanced electrocatalytic activity in fuel cell Xin, Yuchen; Liu, Jian-guo; Zhou, Yong Journal of Power Sources, Vol. 196, Issue 3 https://doi.org/10.1016/j.jpowsour.2010.08.051	journal	February 2011
Multicomponent electrocatalyst with ultralow Pt loading and high hydrogen evolution activity Tiwari, Jitendra N.; Sultan, Siraj; Myung, Chang Woo Nature Energy, Vol. 3, Issue 9 https://doi.org/10.1038/s41560-018-0209-x	journal	July 2018
Synthesis and analysis of thin conducting pyrolytic carbon films McEvoy, Niall; Peltekis, Nikolaos; Kumar, Shishir Carbon, Vol. 50, Issue 3 https://doi.org/10.1016/j.carbon.2011.10.036	journal	March 2012
Self-Assembled Fe-N-Doped Carbon Nanotube Aerogels with Single-Atom Catalyst Feature as High-Efficiency Oxygen Reduction Electrocatalysts Zhu, Chengzhou; Fu, Shaofang; Song, Junhua Small, Vol. 13, Issue 15 https://doi.org/10.1002/smll.201603407	journal	February 2017
A highly active, stable and synergistic Pt nanoparticles/Mo2C nanotube catalyst for methanol electro-oxidation Zhang, Kai; Yang, Wei; Ma, Chao NPG Asia Materials, Vol. 7, Issue 1 https://doi.org/10.1038/am.2014.122	journal	January 2015
Influence of Nitrogen Doping on Oxygen Reduction Electrocatalysis at Carbon Nanofiber Electrodes Maldonado, Stephen; Stevenson, Keith J. The Journal of Physical Chemistry B, Vol. 109, Issue 10, p. 4707-4716 https://doi.org/10.1021/jp044442z	journal	March 2005
Is Ammonium Peroxydisulfate Indispensable for Preparation of Aniline-Derived Iron-Nitrogen-Carbon Electrocatalysts? Xie, Nan-Hong; Yan, Xiang-Hui; Xu, Bo-Qing ChemSusChem, Vol. 9, Issue 17 https://doi.org/10.1002/cssc.201600543	journal	August 2016
Raman scattering of laser-deposited amorphous carbon Bacsa, W. S.; Lannin, J. S.; Pappas, D. L. Physical Review B, Vol. 47, Issue 16 https://doi.org/10.1103/PhysRevB.47.10931	journal	April 1993
Evidence of a Unique Electron Donor−Acceptor Property for Platinum Nanoparticles as Studied by XPS Qiu, Limei; Liu, Fen; Zhao, Liangzhong Langmuir, Vol. 22, Issue 10 https://doi.org/10.1021/la053071q	journal	May 2006
Catalytic Nanoarchitectures--the Importance of Nothing and the Unimportance of Periodicity Rolison, D. R. Science, Vol. 299, Issue 5613 https://doi.org/10.1126/science.1082332	journal	March 2003
Breakdown of the adiabatic Born–Oppenheimer approximation in graphene Pisana, Simone; Lazzeri, Michele; Casiraghi, Cinzia Nature Materials, Vol. 6, Issue 3 https://doi.org/10.1038/nmat1846	journal	February 2007
First-Principles Predictions of Structure–Function Relationships of Graphene-Supported Platinum Nanoclusters Shi, Hongbo; Auerbach, Scott M.; Ramasubramaniam, Ashwin The Journal of Physical Chemistry C, Vol. 120, Issue 22 https://doi.org/10.1021/acs.jpcc.6b01288	journal	May 2016
Raman spectrum of modified PAN-based carbon fibers during graphitization Ko, Tse-Hao Journal of Applied Polymer Science, Vol. 59, Issue 4 https://doi.org/10.1002/(SICI)1097-4628(19960124)59:4<577::AID-APP2>3.0.CO;2-Q	journal	January 1996
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 Wang, Yan-Jie; Zhao, Nana; Fang, Baizeng Chemical Reviews, Vol. 115, Issue 9 https://doi.org/10.1021/cr500519c	journal	April 2015
Ex Situ and In Situ Stability Studies of PEMFC Catalysts Stevens, D. A.; Hicks, M. T.; Haugen, G. M. Journal of The Electrochemical Society, Vol. 152, Issue 12 https://doi.org/10.1149/1.2097361	journal	January 2005
Remarkable support effect of SWNTs in Pt catalyst for methanol electrooxidation Wu, Gang; Chen, Yong-Sheng; Xu, Bo-Qing Electrochemistry Communications, Vol. 7, Issue 12 https://doi.org/10.1016/j.elecom.2005.07.015	journal	December 2005
Nitrogen-doped carbon nanostructures and their composites as catalytic materials for proton exchange membrane fuel cell Shao, Yuyan; Sui, Jiehe; Yin, Geping Applied Catalysis B: Environmental, Vol. 79, Issue 1, p. 89-99 https://doi.org/10.1016/j.apcatb.2007.09.047	journal	February 2008
Purification and structural annealing of multiwalled carbon nanotubes at graphitization temperatures Andrews, R.; Jacques, D.; Qian, D. Carbon, Vol. 39, Issue 11 https://doi.org/10.1016/S0008-6223(00)00301-8	journal	September 2001
Self-crosslinked polyaniline hydrogel electrodes for electrochemical energy storage Guo, Haitao; He, Weina; Lu, Yun Carbon, Vol. 92 https://doi.org/10.1016/j.carbon.2015.03.062	journal	October 2015
Enhancement of Pt and Pt-alloy fuel cell catalyst activity and durability via nitrogen-modified carbon supports Zhou, Yingke; Neyerlin, Kenneth; Olson, Tim S. Energy & Environmental Science, Vol. 3, Issue 10 https://doi.org/10.1039/c003710a	journal	January 2010
Phosphate-Tolerant Oxygen Reduction Catalysts Li, Qing; Wu, Gang; Cullen, David A. ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs500807v	journal	August 2014
Facile Synthesis of Polyaniline-Polypyrrole Nanofibers for Application in Chemical Deposition of Metal Nanoparticles Xu, Ping; Han, Xijiang; Wang, Chao Macromolecular Rapid Communications, Vol. 29, Issue 16 https://doi.org/10.1002/marc.200800173	journal	July 2008
Hydrogel-derived non-precious electrocatalysts for efficient oxygen reduction You, Bo; Yin, Peiqun; Zhang, Junli Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep11739	journal	July 2015
Recent advances in activity and durability enhancement of Pt/C catalytic cathode in PEMFC Yu, Xingwen; Ye, Siyu Journal of Power Sources, Vol. 172, Issue 1 https://doi.org/10.1016/j.jpowsour.2007.07.049	journal	October 2007
Quantitative structural and textural assessment of laminar pyrocarbons through Raman spectroscopy, electron diffraction and few other techniques Vallerot, Jean-Marie; Bourrat, Xavier; Mouchon, Arnaud arXiv https://doi.org/10.48550/arxiv.0707.0214	text	January 2007

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