Synergistic Mn-Co catalyst outperforms Pt on high-rate oxygen reduction for alkaline polymer electrolyte fuel cells

Wang, Ying; Yang, Yao; Jia, Shuangfeng; Wang, Xiaoming; Lyu, Kangjie; Peng, Yanqiu; Zheng, He; Wei, Xing; Ren, Huan; Xiao, Li; Wang, Jianbo; Muller, David A.; Abruña, Héctor D.; Hwang, Bing Joe; Lu, Juntao; Zhuang, Lin

doi:10.1038/s41467-019-09503-4

Title: Synergistic Mn-Co catalyst outperforms Pt on high-rate oxygen reduction for alkaline polymer electrolyte fuel cells

Journal Article · Wed Apr 03 00:00:00 EDT 2019 · Nature Communications

DOI:https://doi.org/10.1038/s41467-019-09503-4· OSTI ID:1566612

Wang, Ying ^[1];

^[2]; Jia, Shuangfeng ^[1]; Wang, Xiaoming ^[3]; Lyu, Kangjie ^[1]; Peng, Yanqiu ^[1];

^[1]; Wei, Xing ^[1]; Ren, Huan ^[1]; Xiao, Li ^[1];

^[1];

^[2];

^[3]; Lu, Juntao ^[1];

^[1]

Wuhan Univ. (China)
Cornell Univ., Ithaca, NY (United States)
National Taiwan Univ., Taipei (Taiwan)

Alkaline polymer electrolyte fuel cells are a class of fuel cells that enable the use of non-precious metal catalysts, particularly for the oxygen reduction reaction at the cathode. While there have been alternative materials exhibiting Pt-comparable activity in alkaline solutions, to the best of our knowledge none have outperformed Pt in fuel-cell tests. Here we report a Mn-Co spinel cathode that can deliver greater power, at high current densities, than a Pt cathode. The power density of the cell employing the Mn-Co cathode reaches 1.1 W cm^-2 at 2.5 A cm^-2 at 60 °C. Moreover, this catalyst outperforms Pt at low humidity. In-depth characterization reveals that the remarkable performance originates from synergistic effects where the Mn sites bind O₂ and the Co sites activate H₂O, so as to facilitate the proton-coupled electron transfer processes. Such an electrocatalytic synergy is pivotal to the high-rate oxygen reduction, particularly under water depletion/low humidity conditions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Alkaline-Based Energy Solutions (CABES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: SC0019445

OSTI ID:: 1566612

Journal Information:: Nature Communications, Vol. 10, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 167 works

Citation information provided by
Web of Science

References (55)

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Fe–N–C Catalyst Graphitic Layer Structure and Fuel Cell Performance Workman, Michael J.; Serov, Alexey; Tsui, Lok-kun ACS Energy Letters, Vol. 2, Issue 7 https://doi.org/10.1021/acsenergylett.7b00391	journal	June 2017
Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction Gong, K.; Du, F.; Xia, Z. Science, Vol. 323, Issue 5915, p. 760-764 https://doi.org/10.1126/science.1168049	journal	February 2009
UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations Rappe, A. K.; Casewit, C. J.; Colwell, K. S. Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035 https://doi.org/10.1021/ja00051a040	journal	December 1992
First-principles prediction of redox potentials in transition-metal compounds with $LDA + U$ Zhou, F.; Cococcioni, M.; Marianetti, C. A. Physical Review B, Vol. 70, Issue 23 https://doi.org/10.1103/PhysRevB.70.235121	journal	December 2004
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts Cheng, Fangyi; Shen, Jian; Peng, Bo Nature Chemistry, Vol. 3, Issue 1 https://doi.org/10.1038/nchem.931	journal	December 2010
High performance aliphatic-heterocyclic benzyl-quaternary ammonium radiation-grafted anion-exchange membranes Ponce-González, Julia; Whelligan, Daniel K.; Wang, Lianqin Energy & Environmental Science, Vol. 9, Issue 12 https://doi.org/10.1039/C6EE01958G	journal	January 2016
Elucidating Proton Involvement in the Rate-Determining Step for Pt/Pd-Based and Non-Precious-Metal Oxygen Reduction Reaction Catalysts Using the Kinetic Isotope Effect Tse, Edmund C. M.; Varnell, Jason A.; Hoang, Thao T. H. The Journal of Physical Chemistry Letters, Vol. 7, Issue 18 https://doi.org/10.1021/acs.jpclett.6b01235	journal	August 2016
Electrochemical reduction of oxygen on platinum nanoparticles in alkaline media Geniès, L.; Faure, R.; Durand, R. Electrochimica Acta, Vol. 44, Issue 8-9 https://doi.org/10.1016/S0013-4686(98)00254-0	journal	December 1998
Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis Li, Chun; Han, Xiaopeng; Cheng, Fangyi Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8345	journal	June 2015
GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers Abraham, Mark James; Murtola, Teemu; Schulz, Roland SoftwareX, Vol. 1-2 https://doi.org/10.1016/j.softx.2015.06.001	journal	September 2015
Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels Wei, Chao; Feng, Zhenxing; Scherer, Günther G. Advanced Materials, Vol. 29, Issue 23 https://doi.org/10.1002/adma.201606800	journal	April 2017
Designing Advanced Alkaline Polymer Electrolytes for Fuel Cell Applications Pan, Jing; Chen, Chen; Zhuang, Lin Accounts of Chemical Research, Vol. 45, Issue 3 https://doi.org/10.1021/ar200201x	journal	October 2011
Electrocatalyst approaches and challenges for automotive fuel cells Debe, Mark K. Nature, Vol. 486, Issue 7401 https://doi.org/10.1038/nature11115	journal	June 2012
Anion-exchange membranes in electrochemical energy systems Varcoe, John R.; Atanassov, Plamen; Dekel, Dario R. Energy & Environmental Science, Vol. 7, Issue 10, p. 3135-3191 https://doi.org/10.1039/C4EE01303D	journal	January 2014
Theory of Coupled Electron and Proton Transfer Reactions Hammes-Schiffer, Sharon; Stuchebrukhov, Alexei A. Chemical Reviews, Vol. 110, Issue 12 https://doi.org/10.1021/cr1001436	journal	December 2010
Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A. Nature Nanotechnology, Vol. 11, Issue 12 https://doi.org/10.1038/nnano.2016.265	journal	December 2016
Rational design of polyaromatic ionomers for alkaline membrane fuel cells with >1 W cm ⁻² power density Maurya, Sandip; Noh, Sangtaik; Matanovic, Ivana Energy & Environmental Science, Vol. 11, Issue 11 https://doi.org/10.1039/C8EE02192A	journal	January 2018
Molecular Dynamic Simulations of the Effect on the Hydration of Nafion in the Presence of a Platinum Nanoparticle Selvan, Myvizhi Esai; He, Qianping; Calvo-Muñoz, Elisa M. The Journal of Physical Chemistry C, Vol. 116, Issue 23 https://doi.org/10.1021/jp3020436	journal	May 2012
Steady state and transient simulation of anion exchange membrane fuel cells Dekel, Dario R.; Rasin, Igal G.; Page, Miles Journal of Power Sources, Vol. 375 https://doi.org/10.1016/j.jpowsour.2017.07.012	journal	January 2018
Pt–Ru catalyzed hydrogen oxidation in alkaline media: oxophilic effect or electronic effect? Wang, Ying; Wang, Gongwei; Li, Guangwei Energy & Environmental Science, Vol. 8, Issue 1 https://doi.org/10.1039/C4EE02564D	journal	January 2015
Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes Ledezma-Yanez, Isis; Wallace, W. David Z.; Sebastián-Pascual, Paula Nature Energy, Vol. 2, Issue 4 https://doi.org/10.1038/nenergy.2017.31	journal	March 2017
Nosé–Hoover chains: The canonical ensemble via continuous dynamics Martyna, Glenn J.; Klein, Michael L.; Tuckerman, Mark The Journal of Chemical Physics, Vol. 97, Issue 4 https://doi.org/10.1063/1.463940	journal	August 1992
Alkaline polymer electrolyte fuel cells stably working at 80 °C Peng, Hanqing; Li, Qihao; Hu, Meixue Journal of Power Sources, Vol. 390 https://doi.org/10.1016/j.jpowsour.2018.04.047	journal	June 2018
Understanding how high-performance anion exchange membrane fuel cells were achieved: Component, interfacial, and cell-level factors Mustain, William E. Current Opinion in Electrochemistry, Vol. 12 https://doi.org/10.1016/j.coelec.2018.11.010	journal	December 2018
Fe/N/C Nanotubes with Atomic Fe Sites: A Highly Active Cathode Catalyst for Alkaline Polymer Electrolyte Fuel Cells Ren, Huan; Wang, Ying; Yang, Yao ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b02340	journal	August 2017
The Spatial Structure in Liquid Water Kusalik, P. G.; Svishchev, I. M. Science, Vol. 265, Issue 5176 https://doi.org/10.1126/science.265.5176.1219	journal	August 1994
Gold Deposition by Galvanic Displacement on Semiconductor Surfaces: Effect of Substrate on Adhesion Magagnin, L.; Maboudian, R.; Carraro, C. The Journal of Physical Chemistry B, Vol. 106, Issue 2 https://doi.org/10.1021/jp013396p	journal	January 2002
Spinels: Controlled Preparation, Oxygen Reduction/Evolution Reaction Application, and Beyond Zhao, Qing; Yan, Zhenhua; Chen, Chengcheng Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00051	journal	July 2017
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction Liang, Yongye; Li, Yanguang; Wang, Hailiang Nature Materials, Vol. 10, Issue 10, p. 780-786 https://doi.org/10.1038/nmat3087	journal	August 2011
Spatially Resolved Quantification of the Surface Reactivity of Solid Catalysts Huang, Bing; Xiao, Li; Lu, Juntao Angewandte Chemie International Edition, Vol. 55, Issue 21 https://doi.org/10.1002/anie.201601824	journal	April 2016
Proton transfer dynamics control the mechanism of O2 reduction by a non-precious metal electrocatalyst Tse, Edmund C. M.; Barile, Christopher J.; Kirchschlager, Nicholas A. Nature Materials, Vol. 15, Issue 7 https://doi.org/10.1038/nmat4636	journal	May 2016
Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution Lu, Fang; Zhang, Yu; Liu, Shizhong Journal of the American Chemical Society, Vol. 139, Issue 21 https://doi.org/10.1021/jacs.7b01735	journal	May 2017
The Magnitude of the Primary Kinetic Isotope Effect for Compounds of Hydrogen and Deuterium. Westheimer, F. H. Chemical Reviews, Vol. 61, Issue 3 https://doi.org/10.1021/cr60211a004	journal	June 1961
Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media Staszak-Jirkovský, Jakub; Subbaraman, Ram; Strmcnik, Dusan ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01779	journal	October 2015
Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9618	journal	October 2015
Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki Nature Chemistry, Vol. 3, Issue 7, p. 546-550 https://doi.org/10.1038/nchem.1069	journal	June 2011
Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis Hong, Wesley T.; Risch, Marcel; Stoerzinger, Kelsey A. Energy & Environmental Science, Vol. 8, Issue 5 https://doi.org/10.1039/C4EE03869J	journal	January 2015
Potential-Dependent Reorientation of Water Molecules at an Electrode/Electrolyte Interface Studied by Surface-Enhanced Infrared Absorption Spectroscopy Ataka, Ken-ichi; Yotsuyanagi, Takao; Osawa, Masatoshi The Journal of Physical Chemistry, Vol. 100, Issue 25 https://doi.org/10.1021/jp953636z	journal	January 1996
Dynamic Processes in Electrochemical Reactions Studied by Surface-Enhanced Infrared Absorption Spectroscopy (SEIRAS) Osawa, Masatoshi Bulletin of the Chemical Society of Japan, Vol. 70, Issue 12 https://doi.org/10.1246/bcsj.70.2861	journal	December 1997
Combining theory and experiment in electrocatalysis: Insights into materials design Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F. Science, Vol. 355, Issue 6321 https://doi.org/10.1126/science.aad4998	journal	January 2017
Constructing ionic highway in alkaline polymer electrolytes Pan, Jing; Chen, Chen; Li, Yao Energy Environ. Sci., Vol. 7, Issue 1 https://doi.org/10.1039/C3EE43275K	journal	January 2014
Characterization of hydroxylated oxide film on iron surfaces and its acid-base properties using XPS Kurbatov, G.; Darque-Ceretti, E.; Aucouturier, M. Surface and Interface Analysis, Vol. 18, Issue 12 https://doi.org/10.1002/sia.740181206	journal	December 1992
Alkaline polymer electrolyte fuel cells completely free from noble metal catalysts Lu, S.; Pan, J.; Huang, A. Proceedings of the National Academy of Sciences, Vol. 105, Issue 52, p. 20611-20614 https://doi.org/10.1073/pnas.0810041106	journal	December 2008
Spatially Resolved Quantification of the Surface Reactivity of Solid Catalysts Huang, Bing; Xiao, Li; Lu, Juntao Angewandte Chemie, Vol. 128, Issue 21 https://doi.org/10.1002/ange.201601824	journal	April 2016
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction Zhou, Jing; Zhang, Linjuan; Huang, Yu-Cheng Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15925-2	journal	April 2020
One-dimensional intergrowths in two-dimensional zeolite nanosheets and their effect on ultra-selective transport Kumar, Prashant; Kim, Dae Woo; Rangnekar, Neel Nature Materials, Vol. 19, Issue 4 https://doi.org/10.1038/s41563-019-0581-3	journal	February 2020
Rational identification and characterisation of peptide ligands for targeting polysialic acid Shastry, Divya G.; Irudayanathan, Flaviyan Jerome; Williams, Asher Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-64088-z	journal	May 2020
First-principles prediction of redox potentials in transition-metal compounds with LDA+U Zhou, Fei; Cococcioni, Matteo; Marianetti, Chris A. arXiv https://doi.org/10.48550/arxiv.cond-mat/0406382	text	January 2004
Novel 1,2,4-triazole analogues as mushroom tyrosinase inhibitors: synthesis, kinetic mechanism, cytotoxicity and computational studies Vanjare, Balasaheb D.; Mahajan, Prasad G.; Dige, Nilam C. Molecular Diversity, Vol. 25, Issue 4 https://doi.org/10.1007/s11030-020-10102-5	journal	May 2020
Molecular basis for assembly of the shieldin complex and its implications for NHEJ Liang, Ling; Feng, Jiawen; Zuo, Peng Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15879-5	journal	April 2020
Deep learning enables rapid identification of potent DDR1 kinase inhibitors Zhavoronkov, Alex; Ivanenkov, Yan A.; Aliper, Alex Nature Biotechnology, Vol. 37, Issue 9 https://doi.org/10.1038/s41587-019-0224-x	journal	September 2019
Structural motifs of water on metal oxide surfaces Mu, Rentao; Zhao, Zhi-jian; Dohnálek, Zdenek Chemical Society Reviews, Vol. 46, Issue 7 https://doi.org/10.1039/c6cs00864j	journal	January 2017

Cited By (7)

Ultrasmall Pd‐Cu‐Pt Trimetallic Twin Icosahedrons Boost the Electrocatalytic Performance of Glycerol Oxidation at the Operating Temperature of Fuel Cells Yang, Fang; Ye, JinYu; Yuan, Qiang Advanced Functional Materials, Vol. 30, Issue 11 https://doi.org/10.1002/adfm.201908235	journal	January 2020
Oxygen Reduction Reactions on Single‐ or Few‐Atom Discrete Active Sites for Heterogeneous Catalysis Sharifi, Tiva; Gracia‐Espino, Eduardo; Chen, Anran Advanced Energy Materials, Vol. 10, Issue 11 https://doi.org/10.1002/aenm.201902084	journal	September 2019
Atomically ordered non-precious Co3Ta intermetallic nanoparticles as high-performance catalysts for hydrazine electrooxidation Feng, Guang; An, Li; Li, Biao Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12509-7	journal	October 2019
Karst landform-featured monolithic electrode for water electrolysis in neutral media Gao, Xueqing; Chen, Yingdong; Sun, Tong Energy & Environmental Science, Vol. 13, Issue 1 https://doi.org/10.1039/c9ee02380a	journal	January 2020
Ultrafine Pt cluster and RuO ₂ heterojunction anode catalysts designed for ultra-low Pt-loading anion exchange membrane fuel cells Wang, Rongyue; Li, Dongguo; Maurya, Sandip Nanoscale Horizons, Vol. 5, Issue 2 https://doi.org/10.1039/c9nh00533a	journal	January 2020
Trimetallic palladium–copper–cobalt alloy wavy nanowires improve ethanol electrooxidation in alkaline medium Zhao, Fengling; Li, Chaozhong; Yuan, Qiang Nanoscale, Vol. 11, Issue 41 https://doi.org/10.1039/c9nr05120a	journal	January 2019
Octahedral spinel electrocatalysts for alkaline fuel cells Yang, Yao; Xiong, Yin; Holtz, Megan E. Proceedings of the National Academy of Sciences, Vol. 116, Issue 49 https://doi.org/10.1073/pnas.1906570116	journal	November 2019

Similar Records

A Strategy for Increasing the Efficiency of the Oxygen Reduction Reaction in Mn-Doped Cobalt Ferrites

Journal Article · Thu Feb 21 00:00:00 EST 2019 · Journal of the American Chemical Society · OSTI ID:1566612

Xiong, Yin; Yang, Yao; Feng, Xinran; +2 more

A completely precious metal–free alkaline fuel cell with enhanced performance using a carbon-coated nickel anode

Journal Article · Mon Mar 21 00:00:00 EDT 2022 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1566612

Gao, Yunfei; Yang, Yao; Schimmenti, Roberto; +12 more

Directed surfaces structures and interfaces for enhanced electrocatalyst activity, selectivity, and stability for energy conversion reactions

Technical Report · Wed Apr 20 00:00:00 EDT 2016 · OSTI ID:1566612

Jaramillo, Thomas F.

Related Subjects

25 ENERGY STORAGE
catalysis (heterogeneous)
electrocatalysis
hydrogen and fuel cells
charge transport
membranes
water
materials and chemistry by design
synthesis (novel materials)

Title: Synergistic Mn-Co catalyst outperforms Pt on high-rate oxygen reduction for alkaline polymer electrolyte fuel cells

Citation Formats

References (55)

Cited By (7)

Similar Records

Related Subjects