Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts

Wan, Wenchao; Zhao, Yonggui; Wei, Shiqian; Triana, Carlos A.; Li, Jingguo; Arcifa, Andrea; Allen, Christopher S.; Cao, Rui; Patzke, Greta R.

doi:10.1038/s41467-021-25811-0

Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts

Journal Article · Wed Sep 22 00:00:00 EDT 2021 · Nature Communications

DOI:https://doi.org/10.1038/s41467-021-25811-0· OSTI ID:2471714

^[1]; Zhao, Yonggui ^[1]; ^[2]; Triana, Carlos A. ^[1]; Li, Jingguo ^[1]; Arcifa, Andrea ^[3]; Allen, Christopher S. ^[4]; Cao, Rui ^[5]; ^[1]

University of Zurich (Switzerland)
Leshan Normal University (China)
Empa, Swiss Federal Institute for Materials Science and Technology, Dübendorf (Switzerland)
Diamond Light Source Ltd, Oxfordshire (United Kingdom); University of Oxford (United Kingdom)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Single-atom catalysts with maximum metal utilization efficiency show great potential for sustainable catalytic applications and fundamental mechanistic studies. We here provide a convenient molecular tailoring strategy based on graphitic carbon nitride as support for the rational design of single-site and dual-site single-atom catalysts. Catalysts with single Fe sites exhibit impressive oxygen reduction reaction activity with a half-wave potential of 0.89 V vs. RHE. We find that the single Ni sites are favorable to promote the key structural reconstruction into bridging Ni-O-Fe bonds in dual-site NiFe SAC. Meanwhile, the newly formed Ni-O-Fe bonds create spin channels for electron transfer, resulting in a significant improvement of the oxygen evolution reaction activity with an overpotential of 270 mV at 10 mA cm^–2. We further reveal that the water oxidation reaction follows a dual-site pathway through the deprotonation of *OH at both Ni and Fe sites, leading to the formation of bridging O₂ atop the Ni-O-Fe sites.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 2471714

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 12; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (70)

Catalysis of a Single Transition Metal Site for Water Oxidation: From Mononuclear Molecules to Single Atoms Zhang, Huayang; Tian, Wenjie; Duan, Xiaoguang Advanced Materials, Vol. 32, Issue 18 https://doi.org/10.1002/adma.201904037	journal	December 2019
Dual Single‐Atomic Ni‐N ₄ and Fe‐N ₄ Sites Constructing Janus Hollow Graphene for Selective Oxygen Electrocatalysis Chen, Jiangyue; Li, Hao; Fan, Chuang Advanced Materials, Vol. 32, Issue 30 https://doi.org/10.1002/adma.202003134	journal	June 2020
Spin‐Related Electron Transfer and Orbital Interactions in Oxygen Electrocatalysis Sun, Yuanmiao; Sun, Shengnan; Yang, Haitao Advanced Materials, Vol. 32, Issue 39 https://doi.org/10.1002/adma.202003297	journal	August 2020
Efficient Hydrogen Evolution of Oxidized Ni‐N ₃ Defective Sites for Alkaline Freshwater and Seawater Electrolysis Zang, Wenjie; Sun, Tao; Yang, Tong Advanced Materials, Vol. 33, Issue 8 https://doi.org/10.1002/adma.202003846	journal	December 2020
Recent Development of Ni/Fe‐Based Micro/Nanostructures toward Photo/Electrochemical Water Oxidation Gao, Rui; Yan, Dongpeng Advanced Energy Materials https://doi.org/10.1002/aenm.201900954	journal	May 2019
Heterogeneous Single Atom Electrocatalysis, Where “Singles” Are “Married” Zang, Wenjie; Kou, Zongkui; Pennycook, Stephen J. Advanced Energy Materials, Vol. 10, Issue 9 https://doi.org/10.1002/aenm.201903181	journal	January 2020
Understanding and Optimizing Ultra‐Thin Coordination Polymer Derivatives with High Oxygen Evolution Performance Zhao, Yonggui; Wan, Wenchao; Chen, Yi Advanced Energy Materials, Vol. 10, Issue 37 https://doi.org/10.1002/aenm.202002228	journal	September 2020
Shifting Oxygen Charge Towards Octahedral Metal: A Way to Promote Water Oxidation on Cobalt Spinel Oxides Sun, Shengnan; Sun, Yuanmiao; Zhou, Ye Angewandte Chemie, Vol. 131, Issue 18 https://doi.org/10.1002/ange.201902114	journal	April 2019
Modulating Single‐Atom Palladium Sites with Copper for Enhanced Ambient Ammonia Electrosynthesis Han, Lili; Ren, Zhouhong; Ou, Pengfei Angewandte Chemie, Vol. 133, Issue 1 https://doi.org/10.1002/ange.202010159	journal	October 2020
Cobalt-Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity Ding, Yuxiao; Klyushin, Alexander; Huang, Xing Angewandte Chemie International Edition, Vol. 57, Issue 13 https://doi.org/10.1002/anie.201711688	journal	February 2018
Deciphering Iron‐Dependent Activity in Oxygen Evolution Catalyzed by Nickel–Iron Layered Double Hydroxide Lee, Seunghwa; Bai, Lichen; Hu, Xile Angewandte Chemie International Edition, Vol. 59, Issue 21 https://doi.org/10.1002/anie.201915803	journal	March 2020
Coordination Tunes Selectivity: Two‐Electron Oxygen Reduction on High‐Loading Molybdenum Single‐Atom Catalysts Tang, Cheng; Jiao, Yan; Shi, Bingyang Angewandte Chemie International Edition, Vol. 59, Issue 23 https://doi.org/10.1002/anie.202003842	journal	April 2020
Spectroscopic and Electrokinetic Evidence for a Bifunctional Mechanism of the Oxygen Evolution Reaction** Bai, Lichen; Lee, Seunghwa; Hu, Xile Angewandte Chemie International Edition, Vol. 60, Issue 6 https://doi.org/10.1002/anie.202011388	journal	December 2020
Overall Oxygen Electrocatalysis on Nitrogen‐Modified Carbon Catalysts: Identification of Active Sites and In Situ Observation of Reactive Intermediates Lin, Yangming; Liu, Zigeng; Yu, Linhui Angewandte Chemie International Edition, Vol. 60, Issue 6 https://doi.org/10.1002/anie.202012615	journal	December 2020
Investigation of multiplet splitting of Fe 2p XPS spectra and bonding in iron compounds Grosvenor, A. P.; Kobe, B. A.; Biesinger, M. C. Surface and Interface Analysis, Vol. 36, Issue 12 https://doi.org/10.1002/sia.1984	journal	January 2004
Spectroscopic studies of iron(III) complexes of D-saccharose and D-glucose in the solid state and in solution Nagy, L.; Gajda, T.; Kürti, J. Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 209, Issue 1 https://doi.org/10.1007/BF02063547	journal	September 1996
Iron(III) complexes of sugar-type ligands Nagy, L.; Burger, K.; Kürti, J. Inorganica Chimica Acta, Vol. 124, Issue 1 https://doi.org/10.1016/S0020-1693(00)82085-X	journal	May 1986
Novel up-conversion carbon quantum dots/α-FeOOH nanohybrids eliminate tetracycline and its related drug resistance in visible-light responsive Fenton system Huang, Siqi; Zhang, Qun; Liu, Pengyu Applied Catalysis B: Environmental, Vol. 263 https://doi.org/10.1016/j.apcatb.2019.118336	journal	April 2020
Interpretation of X-ray photoelectron spectra of carbon-nitride thin films: New insights from in situ XPS Hellgren, Niklas; Haasch, Richard T.; Schmidt, Susann Carbon, Vol. 108 https://doi.org/10.1016/j.carbon.2016.07.017	journal	November 2016
Deconvoluting the XPS spectra for nitrogen-doped chars: An analysis from first principles Ayiania, Michael; Smith, Matthew; Hensley, Alyssa J. R. Carbon, Vol. 162 https://doi.org/10.1016/j.carbon.2020.02.065	journal	June 2020
Mass Transfer Mechanism and Equilibrium Modelling of Hydroxytyrosol Adsorption on Olive Pit–Derived Activated Carbon Eder, Severin; Müller, Katrin; Azzari, Paride Chemical Engineering Journal, Vol. 404 https://doi.org/10.1016/j.cej.2020.126519	journal	January 2021
From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis Medford, Andrew J.; Vojvodic, Aleksandra; Hummelshøj, Jens S. Journal of Catalysis, Vol. 328 https://doi.org/10.1016/j.jcat.2014.12.033	journal	August 2015
Principles determining the activity of magnetic oxides for electron transfer reactions Gracia, Jose; Sharpe, Ryan; Munarriz, Julen Journal of Catalysis, Vol. 361 https://doi.org/10.1016/j.jcat.2018.03.012	journal	May 2018
Transforming Energy with Single-Atom Catalysts Ding, Shipeng; Hülsey, Max J.; Pérez-Ramírez, Javier Joule, Vol. 3, Issue 12 https://doi.org/10.1016/j.joule.2019.09.015	journal	December 2019
Single-Atom Alloy Catalysis Hannagan, Ryan T.; Giannakakis, Georgios; Flytzani-Stephanopoulos, Maria Chemical Reviews https://doi.org/10.1021/acs.chemrev.0c00078	journal	June 2020
Theoretical Understandings of Graphene-based Metal Single-Atom Catalysts: Stability and Catalytic Performance Zhuo, Hong-Ying; Zhang, Xin; Liang, Jin-Xia Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.0c00818	journal	October 2020
Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction Kulkarni, Ambarish; Siahrostami, Samira; Patel, Anjli Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00488	journal	December 2017
Surface Charge and Electrostatic Spin Crossover Effects in CoN ₄ Electrocatalysts Duan, Zhiyao; Henkelman, Graeme ACS Catalysis, Vol. 10, Issue 20 https://doi.org/10.1021/acscatal.0c02458	journal	September 2020
Local Modulation of Single-Atomic Mn Sites for Enhanced Ambient Ammonia Electrosynthesis Han, Lili; Hou, Machuan; Ou, Pengfei ACS Catalysis, Vol. 11, Issue 2 https://doi.org/10.1021/acscatal.0c04102	journal	December 2020
Heterogeneous Co–N/C Electrocatalysts with Controlled Cobalt Site Densities for the Hydrogen Evolution Reaction: Structure–Activity Correlations and Kinetic Insights Sa, Young Jin; Park, Sung O.; Jung, Gwan Yeong ACS Catalysis, Vol. 9, Issue 1 https://doi.org/10.1021/acscatal.8b03446	journal	November 2018
Carbon-Based Single-Atom Catalysts for Advanced Applications Gawande, Manoj B.; Fornasiero, Paolo; Zbořil, Radek ACS Catalysis, Vol. 10, Issue 3 https://doi.org/10.1021/acscatal.9b04217	journal	January 2020
Operando Unraveling of the Structural and Chemical Stability of P-Substituted CoSe ₂ Electrocatalysts toward Hydrogen and Oxygen Evolution Reactions in Alkaline Electrolyte Zhu, Yanping; Chen, Hsiao-Chien; Hsu, Chia-Shuo ACS Energy Letters, Vol. 4, Issue 4 https://doi.org/10.1021/acsenergylett.9b00382	journal	March 2019
Highly Productive Electrosynthesis of Ammonia by Admolecule-Targeting Single Ag Sites Chen, Ying; Guo, Ruijie; Peng, Xianyun ACS Nano, Vol. 14, Issue 6 https://doi.org/10.1021/acsnano.0c01340	journal	June 2020
Bifunctional Single Atom Electrocatalysts: Coordination–Performance Correlations and Reaction Pathways Wan, Wenchao; Triana, Carlos A.; Lan, Jinggang ACS Nano, Vol. 14, Issue 10 https://doi.org/10.1021/acsnano.0c05088	journal	October 2020
Highly Efficient Metal-Free Nitrogen-Doped Nanocarbons with Unexpected Active Sites for Aerobic Catalytic Reactions Lin, Yangming; Liu, Zigeng; Niu, Yiming ACS Nano, Vol. 13, Issue 12 https://doi.org/10.1021/acsnano.9b05856	journal	November 2019
Nitrogen charge distributions in free-base porphyrins, metalloporphyrins, and their reduced analogs observed by x-ray photoelectron spectroscopy Karweik, D. H.; Winograd, N. Inorganic Chemistry, Vol. 15, Issue 10 https://doi.org/10.1021/ic50164a003	journal	October 1976
Operando Identification of the Dynamic Behavior of Oxygen Vacancy-Rich Co ₃ O ₄ for Oxygen Evolution Reaction Xiao, Zhaohui; Huang, Yu-Cheng; Dong, Chung-Li Journal of the American Chemical Society, Vol. 142, Issue 28 https://doi.org/10.1021/jacs.0c00257	journal	June 2020
Atomically Dispersed Ni/α-MoC Catalyst for Hydrogen Production from Methanol/Water Lin, Lili; Yu, Qiaolin; Peng, Mi Journal of the American Chemical Society, Vol. 143, Issue 1 https://doi.org/10.1021/jacs.0c10776	journal	December 2020
Operando Spectroscopic Identification of Active Sites in NiFe Prussian Blue Analogues as Electrocatalysts: Activation of Oxygen Atoms for Oxygen Evolution Reaction Su, Xiaozhi; Wang, Yu; Zhou, Jing Journal of the American Chemical Society, Vol. 140, Issue 36 https://doi.org/10.1021/jacs.8b05294	journal	August 2018
Electrocatalytic Water Oxidation at Quinone-on-Carbon: A Model System Study Lin, Yangming; Wu, Kuang-Hsu; Lu, Qing Journal of the American Chemical Society, Vol. 140, Issue 44 https://doi.org/10.1021/jacs.8b07627	journal	October 2018
A Cobalt–Iron Double-Atom Catalyst for the Oxygen Evolution Reaction Bai, Lichen; Hsu, Chia-Shuo; Alexander, Duncan T. L. Journal of the American Chemical Society, Vol. 141, Issue 36 https://doi.org/10.1021/jacs.9b05268	journal	August 2019
Tuning the Coordination Environment in Single-Atom Catalysts to Achieve Highly Efficient Oxygen Reduction Reactions Zhang, Jinqiang; Zhao, Yufei; Chen, Chen Journal of the American Chemical Society, Vol. 141, Issue 51 https://doi.org/10.1021/jacs.9b09352	journal	December 2019
Theoretical and Spectroscopic Study of Nickel(II) Porphyrin Derivatives Berríos, Cristhian; Cárdenas-Jirón, Gloria I.; Marco, José F. The Journal of Physical Chemistry A, Vol. 111, Issue 14 https://doi.org/10.1021/jp0653961	journal	March 2007
Iridium Oxohydroxide, a Significant Member in the Family of Iridium Oxides. Stoichiometry, Characterization, and Implications in Bioelectrodes Cruz, A. M.; Abad, Ll.; Carretero, N. M. The Journal of Physical Chemistry C, Vol. 116, Issue 8 https://doi.org/10.1021/jp212275q	journal	February 2012
FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes Wei, Haisheng; Liu, Xiaoyan; Wang, Aiqin Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6634	journal	December 2014
Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting Fabbri, Emiliana; Nachtegaal, Maarten; Binninger, Tobias Nature Materials, Vol. 16, Issue 9 https://doi.org/10.1038/nmat4938	journal	July 2017
Regulating the coordination structure of single-atom Fe-NxCy catalytic sites for benzene oxidation Pan, Yuan; Chen, Yinjuan; Wu, Konglin Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12362-8	journal	September 2019
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
In-situ structure and catalytic mechanism of NiFe and CoFe layered double hydroxides during oxygen evolution Dionigi, Fabio; Zeng, Zhenhua; Sinev, Ilya Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16237-1	journal	May 2020
Lattice oxygen activation enabled by high-valence metal sites for enhanced water oxidation Zhang, Ning; Feng, Xiaobin; Rao, Dewei Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17934-7	journal	August 2020
Single atom catalysis: a decade of stunning progress and the promise for a bright future Mitchell, Sharon; Pérez-Ramírez, Javier Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-18182-5	journal	August 2020
Multilayer stabilization for fabricating high-loading single-atom catalysts Zhou, Yazhou; Tao, Xiafang; Chen, Guangbo Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-19599-8	journal	November 2020
Isolated copper single sites for high-performance electroreduction of carbon monoxide to multicarbon products Bao, Haihong; Qiu, Yuan; Peng, Xianyun Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-020-20336-4	journal	January 2021
Elucidating intrinsic contribution of d-orbital states to oxygen evolution electrocatalysis in oxides Yun, Tae Gyu; Heo, Yoon; Bin Bae, Hyung Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-21055-0	journal	February 2021
Iridium single-atom catalyst on nitrogen-doped carbon for formic acid oxidation synthesized using a general host–guest strategy Li, Zhi; Chen, Yuanjun; Ji, Shufang Nature Chemistry, Vol. 12, Issue 8 https://doi.org/10.1038/s41557-020-0473-9	journal	June 2020
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
General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities Fei, Huilong; Dong, Juncai; Feng, Yexin Nature Catalysis, Vol. 1, Issue 1 https://doi.org/10.1038/s41929-017-0008-y	journal	January 2018
Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution Cao, Linlin; Luo, Qiquan; Liu, Wei Nature Catalysis, Vol. 2, Issue 2 https://doi.org/10.1038/s41929-018-0203-5	journal	December 2018
Nitrogen-doped activated carbon for a high energy hybrid supercapacitor Li, Bing; Dai, Fang; Xiao, Qiangfeng Energy & Environmental Science, Vol. 9, Issue 1 https://doi.org/10.1039/C5EE03149D	journal	January 2016
Raman spectroscopy of graphene-based materials and its applications in related devices Wu, Jiang-Bin; Lin, Miao-Ling; Cong, Xin Chemical Society Reviews, Vol. 47, Issue 5 https://doi.org/10.1039/C6CS00915H	journal	January 2018
Frontiers of water oxidation: the quest for true catalysts Li, J.; Güttinger, R.; Moré, R. Chemical Society Reviews, Vol. 46, Issue 20 https://doi.org/10.1039/C7CS00306D	journal	January 2017
Earth-abundant elements doping for robust and stable solar-driven water splitting by FeOOH Yan, Junqing; Li, Ping; Ji, Yujin J. Mater. Chem. A, Vol. 5, Issue 40 https://doi.org/10.1039/C7TA07208B	journal	January 2017
Ferromagnetic ligand holes in cobalt perovskite electrocatalysts as an essential factor for high activity towards oxygen evolution Zhang, Ling; Cheruvathur, Ajin; Biz, Chiara Physical Chemistry Chemical Physics, Vol. 21, Issue 6 https://doi.org/10.1039/C8CP07832G	journal	January 2019
Operando X-ray spectroscopic tracking of self-reconstruction for anchored nanoparticles as high-performance electrocatalysts towards oxygen evolution Song, Sanzhao; Zhou, Jing; Su, Xiaozhi Energy & Environmental Science, Vol. 11, Issue 10 https://doi.org/10.1039/C8EE00773J	journal	January 2018
Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation Zhao, Di; Zhuang, Zewen; Cao, Xing Chemical Society Reviews, Vol. 49, Issue 7 https://doi.org/10.1039/C9CS00869A	journal	January 2020
A theoretical investigation into the first-row transition metal–O ₂ adducts Li, Xiao-Xi; Cho, Kyung-Bin; Nam, Wonwoo Inorganic Chemistry Frontiers, Vol. 6, Issue 8 https://doi.org/10.1039/C9QI00407F	journal	January 2019
Transition metal electrocatalysts encapsulated into N-doped carbon nanotubes on reduced graphene oxide nanosheets: efficient water splitting through synergistic effects Wan, Wenchao; Wei, Shiqian; Li, Jingguo Journal of Materials Chemistry A, Vol. 7, Issue 25 https://doi.org/10.1039/C9TA03213D	journal	January 2019
Molecular and heterogeneous water oxidation catalysts: recent progress and joint perspectives Li, J.; Triana, C. A.; Wan, W. Chemical Society Reviews, Vol. 50, Issue 4 https://doi.org/10.1039/D0CS00978D	journal	January 2021
Surface site density and utilization of platinum group metal (PGM)-free Fe–NC and FeNi–NC electrocatalysts for the oxygen reduction reaction Luo, Fang; Wagner, Stephan; Onishi, Ichiro Chemical Science, Vol. 12, Issue 1 https://doi.org/10.1039/D0SC03280H	journal	January 2021
Spin channel induced directional dependent spin exchange interactions between divacantly substituted Fe atoms in graphene Putnam, R.; Balatsky, A. V.; Haraldsen, J. T. Physical Review B, Vol. 100, Issue 12 https://doi.org/10.1103/PhysRevB.100.125435	journal	September 2019

Similar Records

Defect-Promoted Ni-Based Layer Double Hydroxides with Enhanced Deprotonation Capability for Efficient Biomass Electrooxidation

Journal Article · Wed Sep 20 20:00:00 EDT 2023 · Advanced Materials · OSTI ID:2067633

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Catalysis
Catalytic mechanisms
Chemistry
Science & Technology - Other Topics

Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts

Citation Formats

References (70)

Similar Records

Related Subjects