Fe Stabilization by Intermetallic L10-FePt and Pt Catalysis Enhancement in L10-FePt/Pt Nanoparticles for Efficient Oxygen Reduction Reaction in Fuel Cells

Li, Junrui; Xi, Zheng; Pan, Yung -Tin; Spendelow, Jacob S.; Duchesne, Paul N.; Su, Dong; Li, Qing; Yu, Chao; Yin, Zhouyang; Shen, Bo; Kim, Yu Seung; Zhang, Peng; Sun, Shouheng

doi:10.1021/jacs.7b12829

Title: Fe Stabilization by Intermetallic L1₀-FePt and Pt Catalysis Enhancement in L1₀-FePt/Pt Nanoparticles for Efficient Oxygen Reduction Reaction in Fuel Cells

Journal Article · 07 February 2018 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.7b12829 · OSTI ID:1438309

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Brown Univ., Providence, RI (United States). Dept. of Chemistry
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Dalhousie Univ., Halifax, NS (Canada). Dept. of Chemistry
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Huazhong Univ. of Science and Technology, Hubei (People's Republic of China). School of Materials Science and Engineering

We report in this article a detailed study on how to stabilize a first-row transition metal (M) in an intermetallic L1₀-MPt alloy nanoparticle (NP) structure and how to surround the L1₀-MPt with an atomic layer of Pt to enhance the electrocatalysis of Pt for oxygen reduction reaction (ORR) in fuel cell operation conditions. Using 8 nm FePt NPs as an example, we demonstrate that Fe can be stabilized more efficiently in a core/shell structured L1₀-FePt/Pt with a 5 Å Pt shell. The presence of Fe in the alloy core induces the desired compression of the thin Pt shell, especially the 2 atomic layers of Pt shell, further improving the ORR catalysis. This leads to much enhanced Pt catalysis for ORR in 0.1 M HClO₄ solution (both at room temperature and 60°C) and in the membrane electrode assembly (MEA) at 80°C. The L1₀-FePt/Pt catalyst has a mass activity of 0.7 A/mg_Pt from the half-cell ORR test and shows no obvious mass activity loss after 30,000 potential cycles between 0.6 V and 0.95 V at 80°C in the MEA, meeting the DOE 2020 target (<40% loss in mass activity). Here, we are extending the concept and preparing other L1₀-MPt/Pt NPs, such as L1₀-CoPt/Pt NPs, with reduced NP size as a highly efficient ORR catalyst for automotive fuel cell applications.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22) Scientific User Facilities Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation and Fuels. Hydrogen and Fuel Cell Technologies Office (HFTO); Canadian Light Sources, Inc., Saskatoon, SK (Canada); National Natural Science Foundation of China (NSFC); Materials Genome Initiative

Grant/Contract Number:: SC0012704; AC52-06NA25396; AC02-06CH11357; 21603078; 2016YFB0700600

OSTI ID:: 1438309

Alternate ID(s):: OSTI ID: 1461399

Report Number(s):: BNL-205665-2018-JAAM; LA-UR-18-20293

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 8; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (25)

Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation Borup, Rod; Meyers, Jeremy; Pivovar, Bryan Chemical Reviews, Vol. 107, Issue 10 https://doi.org/10.1021/cr050182l	journal	October 2007
Toward sustainable fuel cells Stephens, Ifan Erfyl Lester; Rossmeisl, Jan; Chorkendorff, Ib Science, Vol. 354, Issue 6318 https://doi.org/10.1126/science.aal3303	journal	December 2016
Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces Stamenkovic, Vojislav R.; Mun, Bongjin Simon; Arenz, Matthias Nature Materials, Vol. 6, Issue 3, p. 241-247 https://doi.org/10.1038/nmat1840	journal	February 2007
Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts Strasser, Peter; Koh, Shirlaine; Anniyev, Toyli Nature Chemistry, Vol. 2, Issue 6 https://doi.org/10.1038/nchem.623	journal	April 2010
Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces Chen, C.; Kang, Y.; Huo, Z. Science, Vol. 343, Issue 6177 https://doi.org/10.1126/science.1249061	journal	February 2014
High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction Huang, X.; Zhao, Z.; Cao, L. Science, Vol. 348, Issue 6240 https://doi.org/10.1126/science.aaa8765	journal	June 2015
Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction Li, Mufan; Zhao, Zipeng; Cheng, Tao Science, Vol. 354, Issue 6318 https://doi.org/10.1126/science.aaf9050	journal	November 2016
Core/Shell Face-Centered Tetragonal FePd/Pd Nanoparticles as an Efficient Non-Pt Catalyst for the Oxygen Reduction Reaction Jiang, Guangming; Zhu, Huiyuan; Zhang, Xu ACS Nano, Vol. 9, Issue 11 https://doi.org/10.1021/acsnano.5b04361	journal	October 2015
Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts Wang, Deli; Xin, Huolin L.; Hovden, Robert Nature Materials, Vol. 12, Issue 1, p. 81-87 https://doi.org/10.1038/nmat3458	journal	October 2012
Structure-Induced Enhancement in Electrooxidation of Trimetallic FePtAu Nanoparticles Zhang, Sen; Guo, Shaojun; Zhu, Huiyuan Journal of the American Chemical Society, Vol. 134, Issue 11 https://doi.org/10.1021/ja300708j	journal	March 2012
New Approach to Fully Ordered fct-FePt Nanoparticles for Much Enhanced Electrocatalysis in Acid Li, Qing; Wu, Liheng; Wu, Gang Nano Letters, Vol. 15, Issue 4 https://doi.org/10.1021/acs.nanolett.5b00320	journal	March 2015
WinXAS a Program for X-ray Absorption Spectroscopy Data Analysis under MS-Windows Ressler, T. Journal of Synchrotron Radiation, Vol. 5, Issue 2, p. 118-122 https://doi.org/10.1107/S0909049597019298	journal	March 1998
Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure Ankudinov, A. L.; Ravel, B.; Rehr, J. J. Physical Review B, Vol. 58, Issue 12 https://doi.org/10.1103/PhysRevB.58.7565	journal	September 1998
Local Structure, Electronic Behavior, and Electrocatalytic Reactivity of CO-Reduced Platinum–Iron Oxide Nanoparticles Duchesne, Paul N.; Chen, Guangxu; Zheng, Nanfeng The Journal of Physical Chemistry C, Vol. 117, Issue 49 https://doi.org/10.1021/jp4093496	journal	November 2013
Reversibility of Pt-Skin and Pt-Skeleton Nanostructures in Acidic Media Durst, Julien; Lopez-Haro, Miguel; Dubau, Laetitia The Journal of Physical Chemistry Letters, Vol. 5, Issue 3 https://doi.org/10.1021/jz4025707	journal	January 2014
Role of Crystalline Defects in Electrocatalysis: CO Adsorption and Oxidation on Stepped Platinum Electrodes As Studied by in situ Infrared Spectroscopy Lebedeva, N. P.; Rodes, A.; Feliu, J. M. The Journal of Physical Chemistry B, Vol. 106, Issue 38 https://doi.org/10.1021/jp0203806	journal	September 2002
Single-atom catalysis of CO oxidation using Pt1/FeOx Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng Nature Chemistry, Vol. 3, Issue 8 https://doi.org/10.1038/nchem.1095	journal	July 2011
Fast Prediction of Adsorption Properties for Platinum Nanocatalysts with Generalized Coordination Numbers Calle-Vallejo, Federico; Martínez, José I.; García-Lastra, Juan M. Angewandte Chemie International Edition, Vol. 53, Issue 32 https://doi.org/10.1002/anie.201402958	journal	June 2014
Atomic-Scale Modeling of Particle Size Effects for the Oxygen Reduction Reaction on Pt Tritsaris, G. A.; Greeley, J.; Rossmeisl, J. Catalysis Letters, Vol. 141, Issue 7 https://doi.org/10.1007/s10562-011-0637-8	journal	June 2011
Size-Dependent Chemical and Magnetic Ordering inL10-FePt Nanoparticles Rong, C. -b.; Li, D.; Nandwana, V. Advanced Materials, Vol. 18, Issue 22 https://doi.org/10.1002/adma.200601904	journal	November 2006
Proton exchange membrane fuel cell from low temperature to high temperature: Material challenges Shao, Yuyan; Yin, Geping; Wang, Zhenbo Journal of Power Sources, Vol. 167, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.02.065	journal	May 2007
Record activity and stability of dealloyed bimetallic catalysts for proton exchange membrane fuel cells Han, Binghong; Carlton, Christopher E.; Kongkanand, Anusorn Energy & Environmental Science, Vol. 8, Issue 1 https://doi.org/10.1039/C4EE02144D	journal	January 2015
Highly Durable and Active PtFe Nanocatalyst for Electrochemical Oxygen Reduction Reaction Chung, Dong Young; Jun, Samuel Woojoo; Yoon, Gabin Journal of the American Chemical Society, Vol. 137, Issue 49 https://doi.org/10.1021/jacs.5b09653	journal	December 2015
Fine-grained and fully ordered intermetallic PtFe catalysts with largely enhanced catalytic activity and durability Du, Xin Xin; He, Yang; Wang, Xiao Xia Energy & Environmental Science, Vol. 9, Issue 8 https://doi.org/10.1039/C6EE01204C	journal	January 2016
Highly durable fuel cell electrodes based on ionomers dispersed in glycerol Kim, Y. S.; Welch, C. F.; Mack, N. H. Phys. Chem. Chem. Phys., Vol. 16, Issue 13 https://doi.org/10.1039/C4CP00496E	journal	January 2014

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