La- and Mn-doped cobalt spinel oxygen evolution catalyst for proton exchange membrane electrolysis

Chong, Lina; Gao, Guoping; Wen, Jianguo; Li, Haixia; Xu, Haiping; Green, Zach; Sugar, Joshua D.; Kropf, A. Jeremy; Xu, Wenqian; Lin, Xiao-Min; Xu, Hui; Wang, Lin-Wang; Liu, Di-Jia

doi:10.1126/science.ade1499

Title: La- and Mn-doped cobalt spinel oxygen evolution catalyst for proton exchange membrane electrolysis

Journal Article · 11 May 2023 · Science

DOI: https://doi.org/10.1126/science.ade1499 · OSTI ID:1999225

^[1];

^[2];

^[3]; Li, Haixia ^[2];

^[1];

^[4]; Sugar, Joshua D. ^[5];

^[1];

^[6];

^[3];

^[4];

^[2];

^[7]

Argonne National Laboratory (ANL), Argonne, IL (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)
Giner Inc., Auburndale, MA (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)

Discovery of earth-abundant electrocatalysts to replace iridium for the oxygen evolution reaction (OER) in a proton exchange membrane water electrolyzer (PEMWE) represents a critical step in reducing the cost for green hydrogen production. Here we report a nanofibrous cobalt spinel catalyst codoped with lanthanum (La) and manganese (Mn) prepared from a zeolitic imidazolate framework embedded in electrospun polymer fiber. The catalyst demonstrated a low overpotential of 353 millivolts at 10 milliamperes per square centimeter and a low degradation for OER over 360 hours in acidic electrolyte. A PEMWE containing this catalyst at the anode demonstrated a current density of 2000 milliamperes per square centimeter at 2.47 volts (Nafion 115 membrane) or 4000 milliamperes per square centimeter at 3.00 volts (Nafion 212 membrane) and low degradation in an accelerated stress test.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; NA0003525

OSTI ID:: 1999225

Alternate ID(s):: OSTI ID: 2311503

Report Number(s):: SAND-2023-04893J; 183567

Journal Information:: Science, Vol. 380, Issue 6645; ISSN 0036-8075

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices McCrory, Charles C. L.; Jung, Suho; Ferrer, Ivonne M. Journal of the American Chemical Society, Vol. 137, Issue 13 https://doi.org/10.1021/ja510442p	journal	March 2015
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Balancing activity, stability and conductivity of nanoporous core-shell iridium/iridium oxide oxygen evolution catalysts Kim, Yong-Tae; Lopes, Pietro Papa; Park, Shin-Ae Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01734-7	journal	November 2017
Strained hybrid perovskite thin films and their impact on the intrinsic stability of perovskite solar cells Zhao, Jingjing; Deng, Yehao; Wei, Haotong Science Advances, Vol. 3, Issue 11 https://doi.org/10.1126/sciadv.aao5616	journal	November 2017
Nanoporous IrO 2 catalyst with enhanced activity and durability for water oxidation owing to its micro/mesoporous structure Li, Guoqiang; Li, Songtao; Xiao, Meiling Nanoscale, Vol. 9, Issue 27 https://doi.org/10.1039/C7NR02899G	journal	January 2017
A low-noble-metal W _1−x Ir _x O _3−δ water oxidation electrocatalyst for acidic media via rapid plasma synthesis Kumari, Sudesh; Ajayi, Babajide Patrick; Kumar, Bijandra Energy & Environmental Science, Vol. 10, Issue 11 https://doi.org/10.1039/C7EE02626A	journal	January 2017
Design of template-stabilized active and earth-abundant oxygen evolution catalysts in acid Huynh, Michael; Ozel, Tuncay; Liu, Chong Chemical Science, Vol. 8, Issue 7 https://doi.org/10.1039/C7SC01239J	journal	January 2017
Enhancing Electrocatalytic Oxygen Reduction on MnO ₂ with Vacancies Cheng, Fangyi; Zhang, Tianran; Zhang, Yi Angewandte Chemie International Edition, Vol. 52, Issue 9 https://doi.org/10.1002/anie.201208582	journal	January 2013
Water oxidation: From mechanisms to limitations Busch, Michael Current Opinion in Electrochemistry, Vol. 9 https://doi.org/10.1016/j.coelec.2018.06.007	journal	June 2018
X-ray absorption spectroscopy to analyze nuclear geometry and electronic structure of biological metal centers?potential and questions examined with special focus on the tetra-nuclear manganese complex of oxygenic photosynthesis Dau, Holger; Liebisch, Peter; Haumann, Michael Analytical and Bioanalytical Chemistry, Vol. 376, Issue 5 https://doi.org/10.1007/s00216-003-1982-2	journal	July 2003
Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis Koper, Marc T. M. Journal of Electroanalytical Chemistry, Vol. 660, Issue 2 https://doi.org/10.1016/j.jelechem.2010.10.004	journal	September 2011
Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren Proceedings of the National Academy of Sciences, Vol. 112, Issue 34 https://doi.org/10.1073/pnas.1507159112	journal	August 2015
Splitting Water with Cobalt Artero, Vincent; Chavarot-Kerlidou, Murielle; Fontecave, Marc Angewandte Chemie International Edition, Vol. 50, Issue 32 https://doi.org/10.1002/anie.201007987	journal	July 2011
Ultrathin Spinel-Structured Nanosheets Rich in Oxygen Deficiencies for Enhanced Electrocatalytic Water Oxidation Bao, Jian; Zhang, Xiaodong; Fan, Bo Angewandte Chemie International Edition, Vol. 54, Issue 25 https://doi.org/10.1002/anie.201502226	journal	May 2015
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
Nano-size layered manganese–calcium oxide as an efficient and biomimetic catalyst for water oxidation under acidic conditions: comparable to platinum Najafpour, Mohammad Mahdi; Leonard, Kevin C.; Fan, Fu-Ren F. Dalton Transactions, Vol. 42, Issue 14 https://doi.org/10.1039/c3dt32864c	journal	January 2013
In situ X-ray absorption spectroscopy of transition metal based water oxidation catalysts van Oversteeg, Christina H. M.; Doan, Hoang Q.; de Groot, Frank M. F. Chemical Society Reviews, Vol. 46, Issue 1 https://doi.org/10.1039/C6CS00230G	journal	January 2017
Highly acid-durable carbon coated Co3O4 nanoarrays as efficient oxygen evolution electrocatalysts Yang, Xiulin; Li, Henan; Lu, Ang-Yu Nano Energy, Vol. 25 https://doi.org/10.1016/j.nanoen.2016.04.035	journal	July 2016
General Formation of Monodisperse IrM (M = Ni, Co, Fe) Bimetallic Nanoclusters as Bifunctional Electrocatalysts for Acidic Overall Water Splitting Pi, Yecan; Shao, Qi; Wang, Pengtang Advanced Functional Materials, Vol. 27, Issue 27 https://doi.org/10.1002/adfm.201700886	journal	May 2017
Effects of the agglomeration state on the Raman properties of Co₃ O₄ nanoparticles Lorite, I.; Romero, J. J.; Fernández, J. F. Journal of Raman Spectroscopy, Vol. 43, Issue 10 https://doi.org/10.1002/jrs.4098	journal	July 2012
Metal Atom‐Doped Co ₃ O ₄ Hierarchical Nanoplates for Electrocatalytic Oxygen Evolution Zhang, Song Lin; Guan, Bu Yuan; Lu, Xue Feng Advanced Materials, Vol. 32, Issue 31 https://doi.org/10.1002/adma.202002235	journal	June 2020
Nature of Activated Manganese Oxide for Oxygen Evolution Huynh, Michael; Shi, Chenyang; Billinge, Simon J. L. Journal of the American Chemical Society, Vol. 137, Issue 47 https://doi.org/10.1021/jacs.5b06382	journal	November 2015
Crystalline nickel manganese antimonate as a stable water-oxidation catalyst in aqueous 1.0 M H ₂ SO ₄ Moreno-Hernandez, Ivan A.; MacFarland, Clara A.; Read, Carlos G. Energy & Environmental Science, Vol. 10, Issue 10 https://doi.org/10.1039/C7EE01486D	journal	January 2017
High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media Kim, Jaemin; Shih, Pei-Chieh; Tsao, Kai-Chieh Journal of the American Chemical Society, Vol. 139, Issue 34 https://doi.org/10.1021/jacs.7b06808	journal	August 2017
Three-dimensional hierarchically porous iridium oxide-nitrogen doped carbon hybrid: An efficient bifunctional catalyst for oxygen evolution and hydrogen evolution reaction in acid Kundu, Manas Kumar; Mishra, Ranjit; Bhowmik, Tanmay International Journal of Hydrogen Energy, Vol. 45, Issue 11 https://doi.org/10.1016/j.ijhydene.2019.12.186	journal	February 2020
Reduced Mesoporous Co ₃ O ₄ Nanowires as Efficient Water Oxidation Electrocatalysts and Supercapacitor Electrodes Wang, Yongcheng; Zhou, Tong; Jiang, Kun Advanced Energy Materials, Vol. 4, Issue 16 https://doi.org/10.1002/aenm.201400696	journal	July 2014
A highly active and stable IrO _x /SrIrO ₃ catalyst for the oxygen evolution reaction Seitz, Linsey C.; Dickens, Colin F.; Nishio, Kazunori Science, Vol. 353, Issue 6303 https://doi.org/10.1126/science.aaf5050	journal	September 2016
Cobalt hexacyanoferrate supported on Sb-doped SnO ₂ as a non-noble catalyst for oxygen evolution in acidic medium Rodríguez-García, Bárbara; Reyes-Carmona, Álvaro; Jiménez-Morales, Ignacio Sustainable Energy & Fuels, Vol. 2, Issue 3 https://doi.org/10.1039/C7SE00512A	journal	January 2018
Investigation of Oxygen Reduction Activity of Catalysts Derived from Co and Co/Zn Methyl-Imidazolate Frameworks in Proton Exchange Membrane Fuel Cells Chong, Lina; Goenaga, Gabriel A.; Williams, Kia ChemElectroChem, Vol. 3, Issue 10 https://doi.org/10.1002/celc.201600163	journal	May 2016
Water oxidation by amorphous cobalt-based oxides: in situ tracking of redox transitions and mode of catalysis Risch, Marcel; Ringleb, Franziska; Kohlhoff, Mike Energy & Environmental Science, Vol. 8, Issue 2 https://doi.org/10.1039/C4EE03004D	journal	January 2015
In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co²⁺ Kanan, M. W.; Nocera, D. G. Science, Vol. 321, Issue 5892, p. 1072-1075 https://doi.org/10.1126/science.1162018	journal	August 2008
Investigation of Aligned Carbon Nanotubes as a Novel Catalytic Electrodes for PEM Fuel Cells Liu, Di-Jia; Yang, Junbing; Gosztola, David J. Fuel Cell Seminar 30, ECS Transactions https://doi.org/10.1149/1.2728997	conference	January 2007
Perspectives on Low-Temperature Electrolysis and Potential for Renewable Hydrogen at Scale Ayers, Katherine; Danilovic, Nemanja; Ouimet, Ryan Annual Review of Chemical and Biomolecular Engineering, Vol. 10, Issue 1 https://doi.org/10.1146/annurev-chembioeng-060718-030241	journal	June 2019
Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution Grimaud, Alexis; Diaz-Morales, Oscar; Han, Binghong Nature Chemistry, Vol. 9, Issue 5 https://doi.org/10.1038/nchem.2695	journal	January 2017
Enhanced Activity of Gold-Supported Cobalt Oxide for the Electrochemical Evolution of Oxygen Yeo, Boon Siang; Bell, Alexis T. Journal of the American Chemical Society, Vol. 133, Issue 14 https://doi.org/10.1021/ja200559j	journal	April 2011
A general synthesis approach for amorphous noble metal nanosheets Wu, Geng; Zheng, Xusheng; Cui, Peixin Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12859-2	journal	October 2019
The stability number as a metric for electrocatalyst stability benchmarking Geiger, Simon; Kasian, Olga; Ledendecker, Marc Nature Catalysis, Vol. 1, Issue 7 https://doi.org/10.1038/s41929-018-0085-6	journal	June 2018
Unraveling the Role of Doping in Selective Stabilization of NaMnO₂ Polymorphs: Combined Theoretical and Experimental Study Shishkin, Maxim; Kumakura, Shinichi; Sato, Syuhei Chemistry of Materials, Vol. 30, Issue 4 https://doi.org/10.1021/acs.chemmater.7b04394	journal	February 2018
Intrinsically stable in situ generated electrocatalyst for long-term oxidation of acidic water at up to 80 °C Chatti, Manjunath; Gardiner, James L.; Fournier, Maxime Nature Catalysis, Vol. 2, Issue 5 https://doi.org/10.1038/s41929-019-0277-8	journal	May 2019
Electrochemical trapping of metastable Mn ³⁺ ions for activation of MnO ₂ oxygen evolution catalysts Morgan Chan, Zamyla; Kitchaev, Daniil A.; Nelson Weker, Johanna Proceedings of the National Academy of Sciences, Vol. 115, Issue 23 https://doi.org/10.1073/pnas.1722235115	journal	May 2018
Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts Huang, Zhen-Feng; Song, Jiajia; Du, Yonghua Nature Energy, Vol. 4, Issue 4 https://doi.org/10.1038/s41560-019-0355-9	journal	March 2019
Crystalline Cobalt Oxide Films for Sustained Electrocatalytic Oxygen Evolution under Strongly Acidic Conditions Mondschein, Jared S.; Callejas, Juan F.; Read, Carlos G. Chemistry of Materials, Vol. 29, Issue 3 https://doi.org/10.1021/acs.chemmater.6b02879	journal	January 2017
The anodic characteristics of manganese dioxide electrodes prepared by thermal decomposition of manganese nitrate Morita, M.; Iwakura, C.; Tamura, H. Electrochimica Acta, Vol. 22, Issue 4 https://doi.org/10.1016/0013-4686(77)85081-0	journal	April 1977
Synthesis and Activities of Rutile IrO ₂ and RuO ₂ Nanoparticles for Oxygen Evolution in Acid and Alkaline Solutions Lee, Youngmin; Suntivich, Jin; May, Kevin J. The Journal of Physical Chemistry Letters, Vol. 3, Issue 3 https://doi.org/10.1021/jz2016507	journal	January 2012
Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico ChemCatChem, Vol. 3, Issue 7 https://doi.org/10.1002/cctc.201000397	journal	March 2011
A unique oxygen ligand environment facilitates water oxidation in hole-doped IrNiOx core–shell electrocatalysts Nong, Hong Nhan; Reier, Tobias; Oh, Hyung-Suk Nature Catalysis, Vol. 1, Issue 11 https://doi.org/10.1038/s41929-018-0153-y	journal	October 2018
The state of the oxygen at the surface of polycrystalline cobalt oxide Jiménez, V. M.; Fernández, A.; Espinós, J. P. Journal of Electron Spectroscopy and Related Phenomena, Vol. 71, Issue 1 https://doi.org/10.1016/0368-2048(94)02238-0	journal	February 1995
Ab initio pseudopotentials for electronic structure calculations of poly-atomic systems using density-functional theory Fuchs, Martin; Scheffler, Matthias Computer Physics Communications, Vol. 119, Issue 1 https://doi.org/10.1016/S0010-4655(98)00201-X	journal	June 1999
Amorphous Metallic NiFeP: A Conductive Bulk Material Achieving High Activity for Oxygen Evolution Reaction in Both Alkaline and Acidic Media Hu, Fei; Zhu, Shengli; Chen, Shuangming Advanced Materials, Vol. 29, Issue 32 https://doi.org/10.1002/adma.201606570	journal	June 2017
The analysis of a plane wave pseudopotential density functional theory code on a GPU machine Jia, Weile; Cao, Zongyan; Wang, Long Computer Physics Communications, Vol. 184, Issue 1 https://doi.org/10.1016/j.cpc.2012.08.002	journal	January 2013
Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti-Stabilized MnO ₂ Frydendal, Rasmus; Paoli, Elisa A.; Chorkendorff, Ib Advanced Energy Materials, Vol. 5, Issue 22 https://doi.org/10.1002/aenm.201500991	journal	August 2015
Importance of Correlation in Determining Electrocatalytic Oxygen Evolution Activity on Cobalt Oxides García-Mota, Mónica; Bajdich, Michal; Viswanathan, Venkatasubramanian The Journal of Physical Chemistry C, Vol. 116, Issue 39 https://doi.org/10.1021/jp306303y	journal	September 2012
Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis Song, Fang; Hu, Xile Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5477	journal	July 2014
Iridium nanoparticles anchored on 3D graphite foam as a bifunctional electrocatalyst for excellent overall water splitting in acidic solution Zhang, Jian; Wang, Gang; Liao, Zhongquan Nano Energy, Vol. 40 https://doi.org/10.1016/j.nanoen.2017.07.054	journal	October 2017
Homogeneously dispersed multimetal oxygen-evolving catalysts Zhang, B.; Zheng, X.; Voznyy, O. Science, Vol. 352, Issue 6283 https://doi.org/10.1126/science.aaf1525	journal	March 2016
Electrochemical Water Oxidation with Cobalt-Based Electrocatalysts from pH 0–14: The Thermodynamic Basis for Catalyst Structure, Stability, and Activity Gerken, James B.; McAlpin, J. Gregory; Chen, Jamie Y. C. Journal of the American Chemical Society, Vol. 133, Issue 36 https://doi.org/10.1021/ja205647m	journal	August 2011
Electrocatalytic Oxygen Evolution Reaction in Acidic Environments - Reaction Mechanisms and Catalysts Reier, Tobias; Nong, Hong Nhan; Teschner, Detre Advanced Energy Materials, Vol. 7, Issue 1 https://doi.org/10.1002/aenm.201601275	journal	October 2016
Self-terminated electrodeposition of iridium electrocatalysts Ahn, Sang Hyun; Tan, Haiyan; Haensch, Mareike Energy & Environmental Science, Vol. 8, Issue 12 https://doi.org/10.1039/C5EE02541A	journal	January 2015
Iridium-based double perovskites for efficient water oxidation in acid media Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12363	journal	August 2016
Beaded Cobalt Oxide Nanoparticles along Carbon Nanotubes: Towards More Highly Integrated Electronic Devices Fu, L.; Liu, Z.; Liu, Y. Advanced Materials, Vol. 17, Issue 2 https://doi.org/10.1002/adma.200400833	journal	January 2005
Water-Plasma-Enabled Exfoliation of Ultrathin Layered Double Hydroxide Nanosheets with Multivacancies for Water Oxidation Liu, Rong; Wang, Yanyong; Liu, Dongdong Advanced Materials, Vol. 29, Issue 30 https://doi.org/10.1002/adma.201701546	journal	June 2017
Intermetallic Ni ₂ Ta Electrocatalyst for the Oxygen Evolution Reaction in Highly Acidic Electrolytes Mondschein, Jared S.; Kumar, Kuldeep; Holder, Cameron F. Inorganic Chemistry, Vol. 57, Issue 10 https://doi.org/10.1021/acs.inorgchem.8b00503	journal	May 2018
Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J. Nature Chemistry, Vol. 10, Issue 1 https://doi.org/10.1038/nchem.2874	journal	October 2017
Filling the oxygen vacancies in Co ₃ O ₄ with phosphorus: an ultra-efficient electrocatalyst for overall water splitting Xiao, Zhaohui; Wang, Yu; Huang, Yu-Cheng Energy & Environmental Science, Vol. 10, Issue 12 https://doi.org/10.1039/C7EE01917C	journal	January 2017
Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis Smith, Rodney D. L.; Prévot, Mathieu S.; Fagan, Randal D. Science, Vol. 340, Issue 6128 https://doi.org/10.1126/science.1233638	journal	March 2013
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
A comprehensive review on PEM water electrolysis Carmo, Marcelo; Fritz, David L.; Mergel, Jürgen International Journal of Hydrogen Energy, Vol. 38, Issue 12, p. 4901-4934 https://doi.org/10.1016/j.ijhydene.2013.01.151	journal	April 2013

Similar Records

A highly active and stable IrO _x /SrIrO ₃ catalyst for the oxygen evolution reaction

Journal Article · 2016 · Science · OSTI ID:1619836

Seitz, Linsey C.; Dickens, Colin F.; Nishio, Kazunori; +8 more

Iridium metallene oxide for acidic oxygen evolution catalysis

Journal Article · 2021 · Nature Communications · OSTI ID:1829286

Dang, Qian; Lin, Haiping; Fan, Zhenglong; +12 more

Homogeneously dispersed multimetal oxygen-evolving catalysts

Journal Article · 2016 · Science · OSTI ID:1355859

Zhang, Bo; Zheng, Xueli; Voznyy, Oleksandr; +22 more

Related Subjects

36 MATERIALS SCIENCE
OER catalyst
water splitting
PEM

Title: La- and Mn-doped cobalt spinel oxygen evolution catalyst for proton exchange membrane electrolysis

Citation Formats

References (67)

Similar Records

Related Subjects