Understanding the Electronic Structure Evolution of Epitaxial LaNi1–xFexO3 Thin Films for Water Oxidation

Wang, Le; Adiga, Prajwal; Zhao, Jiali; Samarakoon, Widitha S.; Stoerzinger, Kelsey A.; Spurgeon, Steven R.; Matthews, Bethany E.; Bowden, Mark E.; Sushko, Peter V.; Kaspar, Tiffany C.; Sterbinsky, George E.; Heald, Steve M.; Wang, Han; Wangoh, Linda W.; Wu, Jinpeng; Guo, Er-Jia; Qian, Haijie; Wang, Jiaou; Varga, Tamas; Thevuthasan, Suntharampillai; Feng, Zhenxing; Yang, Wanli; Du, Yingge; Chambers, Scott A.

doi:10.1021/acs.nanolett.1c02901

Understanding the Electronic Structure Evolution of Epitaxial LaNi_1–xFe_xO₃ Thin Films for Water Oxidation

Journal Article · Tue Sep 21 04:00:00 EDT 2021 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.1c02901· OSTI ID:1897892

^[1]; Adiga, Prajwal ^[2]; Zhao, Jiali ^[3]; Samarakoon, Widitha S. ^[2]; ^[4]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; Sterbinsky, George E. ^[5]; Heald, Steve M. ^[5]; ^[1]; ^[1]; Wu, Jinpeng ^[6]; ^[3]; Qian, Haijie ^[3]; Wang, Jiaou ^[3]; ^[1]; Thevuthasan, Suntharampillai ^[1] more »

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Oregon State Univ., Corvallis, OR (United States)
Chinese Academy of Sciences (CAS), Beijing (China)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Oregon State Univ., Corvallis, OR (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Rare earth nickelates including LaNiO₃ are promising catalysts for water electrolysis to produce oxygen gas. Recent studies report that Fe substitution for Ni can significantly enhance the oxygen evolution reaction (OER) activity of LaNiO₃. However, the role of Fe in increasing the activity remains ambiguous, with potential origins that are both structural and electronic in nature. Here, on the basis of a series of epitaxial LaNi_1-xFe_xO₃ thin films synthesized by molecular beam epitaxy, we report that Fe substitution tunes the Ni oxidation state in LaNi_1-xFe_xO₃ and a volcano-like OER trend is observed, with x = 0.375 being the most active. Spectroscopy and ab initio modeling reveal that high-valent Fe^3+δ cationic species strongly increase the transition-metal (TM) 3d bandwidth via Ni-O-Fe bridges and enhance TM 3d-O 2p hybridization, boosting the OER activity. These studies deepen our understanding of structural and electronic contributions that give rise to enhanced OER activity in perovskite oxides.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-06CH11357; AC02-05CH11231

OSTI ID:: 1897892

Alternate ID(s):: OSTI ID: 1829602

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 19 Vol. 21; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (36)

Tuning Bifunctional Oxygen Electrocatalysts by Changing the A-Site Rare-Earth Element in Perovskite Nickelates Wang, Le; Stoerzinger, Kelsey A.; Chang, Lei Advanced Functional Materials, Vol. 28, Issue 39 https://doi.org/10.1002/adfm.201803712	journal	August 2018
Oxygen Diode Formed in Nickelate Heterostructures by Chemical Potential Mismatch Guo, Er-Jia; Liu, Yaohua; Sohn, Changhee Advanced Materials, Vol. 30, Issue 15 https://doi.org/10.1002/adma.201705904	journal	March 2018
An Amorphous Nickel–Iron‐Based Electrocatalyst with Unusual Local Structures for Ultrafast Oxygen Evolution Reaction Chen, Gao; Zhu, Yanping; Chen, Hao Ming Advanced Materials, Vol. 31, Issue 28 https://doi.org/10.1002/adma.201900883	journal	May 2019
Hole‐Trapping‐Induced Stabilization of Ni ^4 + in SrNiO ₃ /LaFeO ₃ Superlattices Wang, Le; Yang, Zhenzhong; Bowden, Mark E. Advanced Materials, Vol. 32, Issue 45 https://doi.org/10.1002/adma.202005003	journal	October 2020
Tuning the Electronic Structure of LaNiO ₃ through Alloying with Strontium to Enhance Oxygen Evolution Activity Liu, Jishan; Jia, Endong; Wang, Le Advanced Science, Vol. 6, Issue 19 https://doi.org/10.1002/advs.201901073	journal	August 2019
Double Perovskite LaFe _x Ni _{1− x} O ₃ Nanorods Enable Efficient Oxygen Evolution Electrocatalysis Wang, Huaping; Wang, Juan; Pi, Yecan Angewandte Chemie, Vol. 131, Issue 8 https://doi.org/10.1002/ange.201812545	journal	January 2019
Deciphering the oxygen absorption pre‐edge: a caveat on its application for probing oxygen redox reactions in batteries Roychoudhury, Subhayan; Qiao, Ruimin; Zhuo, Zengqing ENERGY & ENVIRONMENTAL MATERIALS https://doi.org/10.1002/eem2.12119	journal	August 2020
Facilitating the Deprotonation of OH to O through Fe ⁴⁺ ‐Induced States in Perovskite LaNiO ₃ Enables a Fast Oxygen Evolution Reaction Fu, Gaoliang; Li, Weiwei; Zhang, Jia‐Ye Small, Vol. 17, Issue 12 https://doi.org/10.1002/smll.202006930	journal	March 2021
The Effect of Oxygen Stoichiometry on Phase Relations and Structure in the System La1-xSrxFeO3-δ (0 ≤ x ≤ 1, 0 ≤ δ ≤ 0.5) Dann, S. E.; Currie, D. B.; Weller, M. T. Journal of Solid State Chemistry, Vol. 109, Issue 1 https://doi.org/10.1006/jssc.1994.1083	journal	March 1994
On the oxidation state of ‘Fe’ in LaFe1−Ni O3 Idrees, M.; Nadeem, M.; Sung, Nark-Eon Chemical Physics Letters, Vol. 612 https://doi.org/10.1016/j.cplett.2014.08.043	journal	September 2014
Tuning Redox Transitions via Inductive Effect in Metal Oxides and Complexes, and Implications in Oxygen Electrocatalysis Kuznetsov, Denis A.; Han, Binghong; Yu, Yang Joule, Vol. 2, Issue 2 https://doi.org/10.1016/j.joule.2017.11.014	journal	February 2018
Understanding the Enhancement Mechanism of A-Site-Deficient La _x NiO ₃ as an Oxygen Redox Catalyst Qiu, Yunsheng; Gao, Rui; Yang, Wenyun Chemistry of Materials, Vol. 32, Issue 5 https://doi.org/10.1021/acs.chemmater.9b04287	journal	February 2020
Dynamic Lattice Oxygen Participation on Perovskite LaNiO ₃ during Oxygen Evolution Reaction Liu, Jishan; Jia, Endong; Stoerzinger, Kelsey A. The Journal of Physical Chemistry C, Vol. 124, Issue 28 https://doi.org/10.1021/acs.jpcc.0c04808	journal	June 2020
Effect of Lattice Strain on the Formation of Ruddlesden–Popper Faults in Heteroepitaxial LaNiO ₃ for Oxygen Evolution Electrocatalysis Bak, Jumi; Bae, Hyung Bin; Oh, Chadol The Journal of Physical Chemistry Letters, Vol. 11, Issue 17 https://doi.org/10.1021/acs.jpclett.0c01426	journal	July 2020
Enhanced Oxygen Evolution Electrocatalysis in Strained A-Site Cation Deficient LaNiO ₃ Perovskite Thin Films Choi, Min-Ju; Kim, Taemin Ludvic; Kim, Jeong Kyu Nano Letters, Vol. 20, Issue 11 https://doi.org/10.1021/acs.nanolett.0c02949	journal	November 2020
Formation of Two-Dimensional Homologous Faults and Oxygen Electrocatalytic Activities in a Perovskite Nickelate Bak, Jumi; Bae, Hyung Bin; Kim, Jaehoon Nano Letters, Vol. 17, Issue 5 https://doi.org/10.1021/acs.nanolett.7b00561	journal	April 2017
Oxygen Vacancy Induced Room-Temperature Metal–Insulator Transition in Nickelate Films and Its Potential Application in Photovoltaics Wang, Le; Dash, Sibashisa; Chang, Lei ACS Applied Materials & Interfaces, Vol. 8, Issue 15 https://doi.org/10.1021/acsami.6b00650	journal	April 2016
Improving Electrocatalysts for Oxygen Evolution Using Ni _x Fe _{3– x} O ₄ /Ni Hybrid Nanostructures Formed by Solvothermal Synthesis Huang, Jinzhen; Han, Jiecai; Wang, Ran ACS Energy Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsenergylett.8b00888	journal	June 2018
An Investigation of Thin-Film Ni–Fe Oxide Catalysts for the Electrochemical Evolution of Oxygen Louie, Mary W.; Bell, Alexis T. Journal of the American Chemical Society, Vol. 135, Issue 33 https://doi.org/10.1021/ja405351s	journal	August 2013
Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation Trotochaud, Lena; Young, Samantha L.; Ranney, James K. Journal of the American Chemical Society, Vol. 136, Issue 18 https://doi.org/10.1021/ja502379c	journal	April 2014
Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO ₃ Perovskites Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W. Journal of the American Chemical Society, Vol. 138, Issue 8 https://doi.org/10.1021/jacs.5b11713	journal	February 2016
Heterointerface engineered electronic and magnetic phases of NdNiO3 thin films Liu, Jian; Kargarian, Mehdi; Kareev, Mikhail Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3714	journal	November 2013
Atomic-scale control of competing electronic phases in ultrathin LaNiO3 King, P. D. C.; Wei, H. I.; Nie, Y. F. Nature Nanotechnology, Vol. 9, Issue 6 https://doi.org/10.1038/nnano.2014.59	journal	April 2014
Exceptional electrocatalytic oxygen evolution via tunable charge transfer interactions in La0.5Sr1.5Ni1−xFexO4±δ Ruddlesden-Popper oxides Forslund, Robin P.; Hardin, William G.; Rong, Xi Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05600-y	journal	August 2018
Atomic-scale perturbation of oxygen octahedra via surface ion exchange in perovskite nickelates boosts water oxidation Bak, Jumi; Bin Bae, Hyung; Chung, Sung-Yoon Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-10838-1	journal	June 2019
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
Tuning electrochemically driven surface transformation in atomically flat LaNiO3 thin films for enhanced water electrolysis Baeumer, Christoph; Li, Jiang; Lu, Qiyang Nature Materials, Vol. 20, Issue 5 https://doi.org/10.1038/s41563-020-00877-1	journal	January 2021
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
Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives Suen, Nian-Tzu; Hung, Sung-Fu; Quan, Quan Chemical Society Reviews, Vol. 46, Issue 2 https://doi.org/10.1039/C6CS00328A	journal	January 2017
Tuning oxygen electrocatalysis via strain on LaNiO ₃ (001) Yuk, Simuck F.; Cooper, Valentino R. Physical Chemistry Chemical Physics, Vol. 21, Issue 9 https://doi.org/10.1039/C8CP02405G	journal	January 2019
Transition from hopping conduction to band conduction in LaFe _x Ni _{1– x} O ₃ Jung, W. H.; Icuchi, E. Philosophical Magazine B, Vol. 73, Issue 6 https://doi.org/10.1080/01418639608240320	journal	June 1996
Electronic structure of La Ni O 3 − x : An in situ soft x-ray photoemission and absorption study Horiba, K.; Eguchi, R.; Taguchi, M. Physical Review B, Vol. 76, Issue 15 https://doi.org/10.1103/PhysRevB.76.155104	journal	October 2007
Quantifying octahedral rotations in strained perovskite oxide films May, S. J.; Kim, J. -W.; Rondinelli, J. M. Physical Review B, Vol. 82, Issue 1 https://doi.org/10.1103/PhysRevB.82.014110	journal	July 2010
Asymmetric Orbital-Lattice Interactions in Ultrathin Correlated Oxide Films Chakhalian, J.; Rondinelli, J. M.; Liu, Jian Physical Review Letters, Vol. 107, Issue 11 https://doi.org/10.1103/PhysRevLett.107.116805	journal	September 2011
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles Suntivich, J.; May, K. J.; Gasteiger, H. A. Science, Vol. 334, Issue 6061 https://doi.org/10.1126/science.1212858	journal	October 2011
Impact of Strontium-Substitution on Oxygen Evolution Reaction of Lanthanum Nickelates in Alkaline Solution Sankannavar, Ravi; Sandeep, K. C.; Kamath, Sachin Journal of The Electrochemical Society, Vol. 165, Issue 15 https://doi.org/10.1149/2.0301815jes	journal	January 2018

Similar Records

Understanding the Electronic Structure Evolution of Epitaxial LaNi1-xFexO3 Thin Films for Water Oxidation

Journal Article · Wed Oct 13 00:00:00 EDT 2021 · Nano Letters · OSTI ID:1829602

Tuning the Electronic Structure of LaNiO ₃ through Alloying with Strontium to Enhance Oxygen Evolution Activity

Journal Article · Wed Aug 07 00:00:00 EDT 2019 · Advanced Science · OSTI ID:1568921

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Fe substitution
LaNiO3
charge transfer
oxygen evolution reaction
spectroscopy

Understanding the Electronic Structure Evolution of Epitaxial LaNi1–xFexO3 Thin Films for Water Oxidation

Citation Formats

References (36)

Similar Records

Related Subjects

Understanding the Electronic Structure Evolution of Epitaxial LaNi_1–xFe_xO₃ Thin Films for Water Oxidation