Single-Iron Site Catalysts with Self-Assembled Dual-size Architecture and Hierarchical Porosity for Proton-Exchange Membrane Fuel Cells
Abstract
Atomically dispersed and nitrogen coordinated single iron site (i.e., FeN4) catalysts (Fe-N-C) are the most promising platinum group metal (PGM)-free cathode for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). However, current Fe-N-C catalysts are limited by the inferior exposure of active FeN4 sites due to the inevitable agglomeration of particles in cathodes. Herein, we report a self-assembled strategy to synthesize the atomically dispersed FeN4 site catalysts with a hierarchically porous matrix derived from dual-size Fe-doped ZIF-8 crystal precursors by using large particles to support small particles. The tailored structure is effective in mitigating the particle migration, agglomeration, and spatial overlap, thereby exposing increased accessible active sites and facilitating mass transport. The best performing catalyst composed of 100 nm “nucleated seed” assembled by 30 nm “satellite” demonstrates exceptional ORR activity in acidic electrolyte and membrane electrode assembly. This work provides new concepts for designing hierarchically porous catalysts with single metal atom dispersion via self-assembly of ZIF-8 crystal precursors with tunable particle sizes and nanostructures.
- Authors:
-
[4];
- Shenzhen Univ. (China); Univ. at Buffalo, NY (United States); State Univ. of New York (SUNY), Buffalo, NY (United States)
- Univ. at Buffalo, NY (United States); State Univ. of New York (SUNY), Buffalo, NY (United States)
- Oregon State Univ., Corvallis, OR (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Univ. of South Carolina, Columbia, SC (United States)
- Shenzhen Univ. (China)
- Northwestern Univ., Evanston, IL (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Northeast Normal Univ., Changchun (China)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; Univ. at Buffalo; State Univ. of New York (SUNY); National Science Foundation (NSF)
- OSTI Identifier:
- 1649998
- Alternate Identifier(s):
- OSTI ID: 1720226; OSTI ID: 1778307
- Report Number(s):
- BNL-216285-2020-JAAM
Journal ID: ISSN 0926-3373
- Grant/Contract Number:
- SC0012704; CBET-1604392; 1804326; EE0008076; AC02-06CH11357; AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Applied Catalysis B: Environmental
- Additional Journal Information:
- Journal Volume: 279; Journal ID: ISSN 0926-3373
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; single metal sites; oxygen reduction; self-assembly architecture; electrocatalysis; fuel cells
Citation Formats
Zhao, Xiaolin, Yang, Xiaoxuan, Wang, Maoyu, Hwang, Sooyeon, Karakalos, Stavros, Chen, Mengjie, Qiao, Zhi, Wang, Lei, Liu, Bin, Ma, Qing, Cullen, David A., Su, Dong, Yang, Haipeng, Zang, Hong-Ying, Feng, Zhenxing, and Wu, Gang. Single-Iron Site Catalysts with Self-Assembled Dual-size Architecture and Hierarchical Porosity for Proton-Exchange Membrane Fuel Cells. United States: N. p., 2020.
Web. doi:10.1016/j.apcatb.2020.119400.
Zhao, Xiaolin, Yang, Xiaoxuan, Wang, Maoyu, Hwang, Sooyeon, Karakalos, Stavros, Chen, Mengjie, Qiao, Zhi, Wang, Lei, Liu, Bin, Ma, Qing, Cullen, David A., Su, Dong, Yang, Haipeng, Zang, Hong-Ying, Feng, Zhenxing, & Wu, Gang. Single-Iron Site Catalysts with Self-Assembled Dual-size Architecture and Hierarchical Porosity for Proton-Exchange Membrane Fuel Cells. United States. https://doi.org/10.1016/j.apcatb.2020.119400
Zhao, Xiaolin, Yang, Xiaoxuan, Wang, Maoyu, Hwang, Sooyeon, Karakalos, Stavros, Chen, Mengjie, Qiao, Zhi, Wang, Lei, Liu, Bin, Ma, Qing, Cullen, David A., Su, Dong, Yang, Haipeng, Zang, Hong-Ying, Feng, Zhenxing, and Wu, Gang. Thu .
"Single-Iron Site Catalysts with Self-Assembled Dual-size Architecture and Hierarchical Porosity for Proton-Exchange Membrane Fuel Cells". United States. https://doi.org/10.1016/j.apcatb.2020.119400. https://www.osti.gov/servlets/purl/1649998.
@article{osti_1649998,
title = {Single-Iron Site Catalysts with Self-Assembled Dual-size Architecture and Hierarchical Porosity for Proton-Exchange Membrane Fuel Cells},
author = {Zhao, Xiaolin and Yang, Xiaoxuan and Wang, Maoyu and Hwang, Sooyeon and Karakalos, Stavros and Chen, Mengjie and Qiao, Zhi and Wang, Lei and Liu, Bin and Ma, Qing and Cullen, David A. and Su, Dong and Yang, Haipeng and Zang, Hong-Ying and Feng, Zhenxing and Wu, Gang},
abstractNote = {Atomically dispersed and nitrogen coordinated single iron site (i.e., FeN4) catalysts (Fe-N-C) are the most promising platinum group metal (PGM)-free cathode for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). However, current Fe-N-C catalysts are limited by the inferior exposure of active FeN4 sites due to the inevitable agglomeration of particles in cathodes. Herein, we report a self-assembled strategy to synthesize the atomically dispersed FeN4 site catalysts with a hierarchically porous matrix derived from dual-size Fe-doped ZIF-8 crystal precursors by using large particles to support small particles. The tailored structure is effective in mitigating the particle migration, agglomeration, and spatial overlap, thereby exposing increased accessible active sites and facilitating mass transport. The best performing catalyst composed of 100 nm “nucleated seed” assembled by 30 nm “satellite” demonstrates exceptional ORR activity in acidic electrolyte and membrane electrode assembly. This work provides new concepts for designing hierarchically porous catalysts with single metal atom dispersion via self-assembly of ZIF-8 crystal precursors with tunable particle sizes and nanostructures.},
doi = {10.1016/j.apcatb.2020.119400},
journal = {Applied Catalysis B: Environmental},
number = ,
volume = 279,
place = {United States},
year = {Thu Aug 06 00:00:00 EDT 2020},
month = {Thu Aug 06 00:00:00 EDT 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Fe–N–C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells
journal, March 2019
- Wan, Xin; Liu, Xiaofang; Li, Yongcheng
- Nature Catalysis, Vol. 2, Issue 3
Fe-Doped Metal-Organic Frameworks-Derived Electrocatalysts for Oxygen Reduction Reaction in Alkaline Media
journal, January 2018
- Zhao, Xiaolin; Chen, Mengjie; Zuo, Jiandong
- Journal of The Electrochemical Society, Vol. 165, Issue 16
Engineering nanostructures of PGM-free oxygen-reduction catalysts using metal-organic frameworks
journal, January 2017
- Zhang, Hanguang; Osgood, Hannah; Xie, Xiaohong
- Nano Energy, Vol. 31
Nanostructured Nonprecious Metal Catalysts for Oxygen Reduction Reaction
journal, April 2013
- Wu, Gang; Zelenay, Piotr
- Accounts of Chemical Research, Vol. 46, Issue 8
Durability challenges and perspective in the development of PGM-free electrocatalysts for the oxygen reduction reaction
journal, June 2018
- Martinez, Ulises; Komini Babu, Siddharth; Holby, Edward F.
- Current Opinion in Electrochemistry, Vol. 9
Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation
journal, July 2019
- Wang, Xiao Xia; Swihart, Mark T.; Wu, Gang
- Nature Catalysis, Vol. 2, Issue 7
Platinum-group-metal catalysts for proton exchange membrane fuel cells: From catalyst design to electrode structure optimization
journal, January 2020
- Hou, Junbo; Yang, Min; Ke, Changchun
- EnergyChem, Vol. 2, Issue 1
Current progress of Pt and Pt-based electrocatalysts used for fuel cells
journal, January 2020
- Ren, Xuefeng; Lv, Qianyuan; Liu, Lifen
- Sustainable Energy & Fuels, Vol. 4, Issue 1
Pt alloy oxygen-reduction electrocatalysts: Synthesis, structure, and property
journal, May 2020
- Wang, Xiao Xia; Sokolowski, Joshua; Liu, Hui
- Chinese Journal of Catalysis, Vol. 41, Issue 5
Engineering Favorable Morphology and Structure of Fe-N-C Oxygen-Reduction Catalysts through Tuning of Nitrogen/Carbon Precursors
journal, January 2017
- Gupta, Shiva; Zhao, Shuai; Ogoke, Ogechi
- ChemSusChem, Vol. 10, Issue 4
A general dual-templating approach to biomass-derived hierarchically porous heteroatom-doped carbon materials for enhanced electrocatalytic oxygen reduction
journal, January 2019
- Li, Xiaoge; Guan, Bu Yuan; Gao, Shuyan
- Energy & Environmental Science, Vol. 12, Issue 2
Iron Single Atoms on Graphene as Nonprecious Metal Catalysts for High‐Temperature Polymer Electrolyte Membrane Fuel Cells
journal, March 2019
- Cheng, Yi; He, Shuai; Lu, Shanfu
- Advanced Science, Vol. 6, Issue 10
Understanding the High Activity of Fe–N–C Electrocatalysts in Oxygen Reduction: Fe/Fe 3 C Nanoparticles Boost the Activity of Fe–N x
journal, March 2016
- Jiang, Wen-Jie; Gu, Lin; Li, Li
- Journal of the American Chemical Society, Vol. 138, Issue 10
Ordered Pt 3 Co Intermetallic Nanoparticles Derived from Metal–Organic Frameworks for Oxygen Reduction
journal, June 2018
- Wang, Xiao Xia; Hwang, Sooyeon; Pan, Yung-Tin
- Nano Letters, Vol. 18, Issue 7
Metal-Nitrogen-Carbon Catalysts for Oxygen Reduction in PEM Fuel Cells: Self-Template Synthesis Approach to Enhancing Catalytic Activity and Stability
journal, March 2019
- He, Yanghua; Tan, Qiang; Lu, Leilei
- Electrochemical Energy Reviews, Vol. 2, Issue 2
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation
journal, September 2017
- Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu
- Journal of the American Chemical Society, Vol. 139, Issue 40
Atomically Dispersed Iron Cathode Catalysts Derived from Binary Ligand-Based Zeolitic Imidazolate Frameworks with Enhanced Stability for PEM Fuel Cells
journal, January 2019
- Zhang, Hanguang; Ding, Shuo; Hwang, Sooyeon
- Journal of The Electrochemical Society, Vol. 166, Issue 7
Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN 4 Sites for Oxygen Reduction
journal, November 2019
- Li, Jiazhan; Zhang, Hanguang; Samarakoon, Widitha
- Angewandte Chemie International Edition, Vol. 58, Issue 52
Highly active atomically dispersed CoN 4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy
journal, January 2019
- He, Yanghua; Hwang, Sooyeon; Cullen, David A.
- Energy & Environmental Science, Vol. 12, Issue 1
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
Efficient Oxygen Reduction Reaction (ORR) Catalysts Based on Single Iron Atoms Dispersed on a Hierarchically Structured Porous Carbon Framework
journal, June 2018
- Zhang, Zhengping; Sun, Junting; Wang, Feng
- Angewandte Chemie International Edition, Vol. 57, Issue 29
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
Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review
journal, January 2018
- Chen, Mengjie; Wang, Lei; Yang, Haipeng
- Journal of Power Sources, Vol. 375
Directly converting Fe-doped metal–organic frameworks into highly active and stable Fe-N-C catalysts for oxygen reduction in acid
journal, July 2016
- Wang, Xiaojuan; Zhang, Hanguang; Lin, Honghong
- Nano Energy, Vol. 25
Unbalanced MOF-on-MOF growth for the production of a lopsided core–shell of MIL-88B@MIL-88A with mismatched cell parameters
journal, January 2019
- Kim, Dooyoung; Lee, Gihyun; Oh, Sojin
- Chemical Communications, Vol. 55, Issue 1
Supported and coordinated single metal site electrocatalysts
journal, March 2020
- Shi, Qiurong; Hwang, Sooyeon; Yang, Haipeng
- Materials Today
Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N 2 and H 2 O
journal, February 2020
- Mukherjee, Shreya; Yang, Xiaoxuan; Shan, Weitao
- Small Methods, Vol. 4, Issue 6
Atomically dispersed metal–nitrogen–carbon catalysts for fuel cells: advances in catalyst design, electrode performance, and durability improvement
journal, January 2020
- He, Yanghua; Liu, Shengwen; Priest, Cameron
- Chemical Society Reviews, Vol. 49, Issue 11
A dual-metal–organic-framework derived electrocatalyst for oxygen reduction
journal, January 2016
- Guan, Bu Yuan; Yu, Le; (David) Lou, Xiong Wen
- Energy & Environmental Science, Vol. 9, Issue 10
MOF derived catalysts for electrochemical oxygen reduction
journal, January 2014
- Wang, Xiaojuan; Zhou, Junwen; Fu, He
- J. Mater. Chem. A, Vol. 2, Issue 34
Preparation of Fe–N–C catalysts with FeN x ( x = 1, 3, 4) active sites and comparison of their activities for the oxygen reduction reaction and performances in proton exchange membrane fuel cells
journal, January 2019
- Li, Yongcheng; Liu, Xiaofang; Zheng, Lirong
- Journal of Materials Chemistry A, Vol. 7, Issue 45
Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network
journal, August 2015
- Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 34
Is the rapid initial performance loss of Fe/N/C non precious metal catalysts due to micropore flooding?
journal, January 2017
- Choi, Ja-Yeon; Yang, Lijun; Kishimoto, Takeaki
- Energy & Environmental Science, Vol. 10, Issue 1
Ultrathin Hierarchical Porous Carbon Nanosheets for High-Performance Supercapacitors and Redox Electrolyte Energy Storage
journal, March 2018
- Jayaramulu, Kolleboyina; Dubal, Deepak P.; Nagar, Bhawna
- Advanced Materials, Vol. 30, Issue 15
Scalable 2D Hierarchical Porous Carbon Nanosheets for Flexible Supercapacitors with Ultrahigh Energy Density
journal, January 2018
- Yao, Lei; Wu, Qin; Zhang, Peixin
- Advanced Materials, Vol. 30, Issue 11
Hierarchically Porous M-N-C (M = Co and Fe) Single-Atom Electrocatalysts with Robust MN x Active Moieties Enable Enhanced ORR Performance
journal, August 2018
- Zhu, Chengzhou; Shi, Qiurong; Xu, Bo Z.
- Advanced Energy Materials, Vol. 8, Issue 29
Simple-Cubic Carbon Frameworks with Atomically Dispersed Iron Dopants toward High-Efficiency Oxygen Reduction
journal, February 2017
- Wang, Biwei; Wang, Xinxia; Zou, Jinxiang
- Nano Letters, Vol. 17, Issue 3
Ion Transport Behavior in Triblock Copolymer-Templated Ordered Mesoporous Carbons with Different Pore Symmetries
journal, October 2010
- Sun, Gangwei; Wang, Jitong; Liu, Xiaojun
- The Journal of Physical Chemistry C, Vol. 114, Issue 43
Single-atomic cobalt sites embedded in hierarchically ordered porous nitrogen-doped carbon as a superior bifunctional electrocatalyst
journal, November 2018
- Sun, Tingting; Zhao, Shu; Chen, Wenxing
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 50
Nanowire-Directed Templating Synthesis of Metal–Organic Framework Nanofibers and Their Derived Porous Doped Carbon Nanofibers for Enhanced Electrocatalysis
journal, October 2014
- Zhang, Wang; Wu, Zhen-Yu; Jiang, Hai-Long
- Journal of the American Chemical Society, Vol. 136, Issue 41
Nanoreactor Based on Macroporous Single Crystals of Metal-Organic Framework
journal, September 2016
- Wang, Shuhai; Fan, Yanan; Teng, Jun
- Small, Vol. 12, Issue 41
High-performance fuel cell cathodes exclusively containing atomically dispersed iron active sites
journal, January 2019
- Zhang, Hanguang; Chung, Hoon T.; Cullen, David A.
- Energy & Environmental Science, Vol. 12, Issue 8
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
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
High Power Density Platinum Group Metal-free Cathodes for Polymer Electrolyte Fuel Cells
journal, December 2019
- Uddin, Aman; Dunsmore, Lisa; Zhang, Hanguang
- ACS Applied Materials & Interfaces, Vol. 12, Issue 2
In Situ X-ray Absorption Spectroscopy Studies of Nanoscale Electrocatalysts
journal, June 2019
- Wang, Maoyu; Árnadóttir, Líney; Xu, Zhichuan J.
- Nano-Micro Letters, Vol. 11, Issue 1
Role of Local Carbon Structure Surrounding FeN 4 Sites in Boosting the Catalytic Activity for Oxygen Reduction
journal, May 2017
- Liu, Kexi; Wu, Gang; Wang, Guofeng
- The Journal of Physical Chemistry C, Vol. 121, Issue 21
Atomically Dispersed Metal Catalysts for Oxygen Reduction
journal, June 2019
- Chen, Mengjie; He, Yanghua; Spendelow, Jacob S.
- ACS Energy Letters, Vol. 4, Issue 7
Rational design of electrocatalysts and photo(electro)catalysts for nitrogen reduction to ammonia (NH 3 ) under ambient conditions
journal, January 2018
- Guo, Chunxian; Ran, Jingrun; Vasileff, Anthony
- Energy & Environmental Science, Vol. 11, 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
Highly Active and Stable Graphene Tubes Decorated with FeCoNi Alloy Nanoparticles via a Template-Free Graphitization for Bifunctional Oxygen Reduction and Evolution
journal, August 2016
- Gupta, Shiva; Qiao, Liang; Zhao, Shuai
- Advanced Energy Materials, Vol. 6, Issue 22
Carbon nanocomposite catalysts for oxygen reduction and evolution reactions: From nitrogen doping to transition-metal addition
journal, November 2016
- Wu, Gang; Santandreu, Ana; Kellogg, William
- Nano Energy, Vol. 29
Iron Carbide Nanoparticles Encapsulated in Mesoporous Fe-N-Doped Carbon Nanofibers for Efficient Electrocatalysis
journal, May 2015
- Wu, Zhen-Yu; Xu, Xing-Xing; Hu, Bi-Cheng
- Angewandte Chemie International Edition, Vol. 54, Issue 28
3D Porous Fe/N/C Spherical Nanostructures As High-Performance Electrocatalysts for Oxygen Reduction in Both Alkaline and Acidic Media
journal, October 2017
- Wei, Qiliang; Zhang, Gaixia; Yang, Xiaohua
- ACS Applied Materials & Interfaces, Vol. 9, Issue 42
PGM‐Free Cathode Catalysts for PEM Fuel Cells: A Mini‐Review on Stability Challenges
journal, December 2018
- Shao, Yuyan; Dodelet, Jean‐Pol; Wu, Gang
- Advanced Materials, Vol. 31, Issue 31