Structure and Reactivity of Pristine and Reduced Spinel CoFe2O4 (001)/(100) Surfaces

Rushiti, Arjeta; Hättig, Christof; Wen, Bo; Selloni, Annabella

doi:10.1021/acs.jpcc.1c01881

Title: Structure and Reactivity of Pristine and Reduced Spinel CoFe₂O₄ (001)/(100) Surfaces

Journal Article · Mon May 03 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c01881· OSTI ID:1838126

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Ruhr Univ., Bochum (Germany)
Princeton Univ., NJ (United States); Henan Univ., Kaifeng (China)
Princeton Univ., NJ (United States)

Cobalt ferrite, CoFe₂O₄ (CFO), nanocrystals are efficient and competitive anode materials in the field of electrochemical water splitting. Using density functional theory with on-site Hubbard U corrections (DFT+U), we have investigated the structural, electronic and magnetic properties of CFO (001)/(100) surfaces, as well as their reactivities towards water adsorption. Special attention has been focused on the formation of oxygen vacancies (V_O), due to their key role in the oxidation activity of metal oxides, often based on the Mars-van-Krevelen mechanism. Our results show that vacancy formation is easiest at oxygen sites that are not bound to tetrahedrally-coordinated Fe. Water adsorbs mainly in molecular form on the Co/Fe metal cations, whereas it dissociates at defects. In comparison to other spinels, CFO is similar to NiFe₂O₄, exhibiting relatively low energy cost of V_O formation and a strong affinity of the vacancies towards water. Furthermore, these findings suggest that CFO may be a more promising oxidation catalyst than NiCo₂O₄ and Co₃O₄.

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0007347

OSTI ID:: 1838126

Journal Information:: Journal of Physical Chemistry. C, Vol. 125, Issue 18; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

Confinement-induced metal-to-insulator transition in strained LaNiO $_{3}$ /LaAlO $_{3}$ superlattices Blanca-Romero, Ariadna; Pentcheva, Rossitza Physical Review B, Vol. 84, Issue 19 https://doi.org/10.1103/PhysRevB.84.195450	journal	November 2011
Oxygen Deficiency and Reactivity of Spinel NiCo ₂ O ₄ (001) Surfaces Shi, Xiao; Bernasek, Steven L.; Selloni, Annabella The Journal of Physical Chemistry C, Vol. 121, Issue 7 https://doi.org/10.1021/acs.jpcc.6b12005	journal	February 2017
High Temperature Water Gas Shift Reaction over Nanocrystalline Copper Codoped-Modified Ferrites Reddy, Gunugunuri K.; Gunasekera, Kapila; Boolchand, P. The Journal of Physical Chemistry C, Vol. 115, Issue 15 https://doi.org/10.1021/jp2003084	journal	March 2011
Magnetic Properties and Mössbauer Spectroscopy of Fe ₃ O ₄ /CoFe ₂ O ₄ Nanorods Hähsler, Martin; Landers, Joachim; Nowack, Tim Inorganic Chemistry, Vol. 59, Issue 6 https://doi.org/10.1021/acs.inorgchem.9b03267	journal	February 2020
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
Tuning of optical bandgap and magnetization of CoFe ₂ O ₄ thin films Sharma, Deepanshu; Khare, Neeraj Applied Physics Letters, Vol. 105, Issue 3 https://doi.org/10.1063/1.4890863	journal	July 2014
Unravelling the Role of Metallic Cu in Cu-CuFe ₂ O ₄ /C Nanohybrid for Enhanced Oxygen Reduction Electrocatalysis Borah, Biraj Jyoti; Yamada, Yusuke; Bharali, Pankaj ACS Applied Energy Materials, Vol. 3, Issue 4 https://doi.org/10.1021/acsaem.0c00006	journal	March 2020
Surface Termination and Composition Control of Activity of the Co _x Ni _{1– x} Fe ₂ O ₄ (001) Surface for Water Oxidation: Insights from DFT+ U Calculations Hajiyani, Hamidreza; Pentcheva, Rossitza ACS Catalysis, Vol. 8, Issue 12 https://doi.org/10.1021/acscatal.8b00574	journal	October 2018
Probing optical band gaps at the nanoscale in NiFe ₂ O ₄ and CoFe ₂ O ₄ epitaxial films by high resolution electron energy loss spectroscopy Dileep, K.; Loukya, B.; Pachauri, N. Journal of Applied Physics, Vol. 116, Issue 10 https://doi.org/10.1063/1.4895059	journal	September 2014
Formation, Electronic Structure, and Defects of Ni Substituted Spinel Cobalt Oxide: a DFT+U Study Shi, Xiao; Bernasek, Steven L.; Selloni, Annabella The Journal of Physical Chemistry C, Vol. 120, Issue 27 https://doi.org/10.1021/acs.jpcc.6b03096	journal	June 2016
The Role of Composition of Uniform and Highly Dispersed Cobalt Vanadium Iron Spinel Nanocrystals for Oxygen Electrocatalysis Chakrapani, Kalapu; Bendt, Georg; Hajiyani, Hamidreza ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03529	journal	January 2018
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502 https://doi.org/10.1088/0953-8984/21/39/395502	journal	September 2009
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
N2O catalytic decomposition over various spinel-type oxides Russo, Nunzio; Fino, Debora; Saracco, Guido Catalysis Today, Vol. 119, Issue 1-4 https://doi.org/10.1016/j.cattod.2006.08.012	journal	January 2007
Tailoring Morphology and Electronic Structure of Cobalt Iron Oxide Nanowires for Electrochemical Oxygen Evolution Reaction Budiyanto, Eko; Yu, Mingquan; Chen, Minmin ACS Applied Energy Materials, Vol. 3, Issue 9 https://doi.org/10.1021/acsaem.0c01201	journal	August 2020
Thermodynamic Stability, Redox Properties, and Reactivity of Mn ₃ O ₄ , Fe ₃ O ₄ , and Co ₃ O ₄ Model Catalysts for N ₂ O Decomposition: Resolving the Origins of Steady Turnover Kaczmarczyk, Jan; Zasada, Filip; Janas, Janusz ACS Catalysis, Vol. 6, Issue 2 https://doi.org/10.1021/acscatal.5b02642	journal	January 2016
2D Nanostructures of CoFe2O4 and NiFe2O4: Efficient Oxygen Evolution Catalyst Mahala, Chavi; Sharma, Mamta Devi; Basu, Mrinmoyee Electrochimica Acta, Vol. 273 https://doi.org/10.1016/j.electacta.2018.04.079	journal	May 2018
Role of Composition and Size of Cobalt Ferrite Nanocrystals in the Oxygen Evolution Reaction Chakrapani, Kalapu; Bendt, Georg; Hajiyani, Hamidreza ChemCatChem, Vol. 9, Issue 15 https://doi.org/10.1002/cctc.201700376	journal	June 2017
Selective 2-Propanol Oxidation over Unsupported Co ₃ O ₄ Spinel Nanoparticles: Mechanistic Insights into Aerobic Oxidation of Alcohols Anke, Sven; Bendt, Georg; Sinev, Ilya ACS Catalysis, Vol. 9, Issue 7 https://doi.org/10.1021/acscatal.9b01048	journal	May 2019
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism Vanderbilt, David Physical Review B, Vol. 41, Issue 11, p. 7892-7895 https://doi.org/10.1103/PhysRevB.41.7892	journal	April 1990
Single-crystal elastic constants of Co-Al and Co-Fe spinels Li, Z.; Fisher, E. S.; Liu, J. Z. Journal of Materials Science, Vol. 26, Issue 10 https://doi.org/10.1007/BF02387728	journal	May 1991
Mechanism and activity of CO oxidation on (001) and (110) surfaces of spinel Co3O4, NiCo2O4 and NiFe2O4: A DFT + U study Shi, Xiao; Bernasek, Steven L.; Selloni, Annabella Surface Science, Vol. 677 https://doi.org/10.1016/j.susc.2018.08.002	journal	November 2018
DFT+U Study of the Surface Structure and Stability of Co ₃ O ₄ (110): Dependence on U Selcuk, Sencer; Selloni, Annabella The Journal of Physical Chemistry C, Vol. 119, Issue 18 https://doi.org/10.1021/acs.jpcc.5b02298	journal	April 2015
On the reversible deactivation of cobalt ferrite spinel nanoparticles applied in selective 2-propanol oxidation Anke, Sven; Falk, Tobias; Bendt, Georg Journal of Catalysis, Vol. 382 https://doi.org/10.1016/j.jcat.2019.12.007	journal	February 2020
In Situ Characterization of CuFe ₂ O ₄ and Cu/Fe ₃ O ₄ Water−Gas Shift Catalysts Estrella, Michael; Barrio, Laura; Zhou, Gong The Journal of Physical Chemistry C, Vol. 113, Issue 32 https://doi.org/10.1021/jp903818q	journal	July 2009
Structural, electronic and magnetic properties of partially inverse spinel CoFe ₂ O ₄ : a first-principles study Hou, Y. H.; Zhao, Y. J.; Liu, Z. W. Journal of Physics D: Applied Physics, Vol. 43, Issue 44 https://doi.org/10.1088/0022-3727/43/44/445003	journal	October 2010
In situ studies of surface of NiFe2O4 catalyst during complete oxidation of methane Zhang, Shiran; Shan, Junjun; Nie, Longhui Surface Science, Vol. 648 https://doi.org/10.1016/j.susc.2015.12.011	journal	June 2016
Controlling the electronic structure of Co $_{1 - x} {Fe}_{2 + x}$ O $_{4}$ thin films through iron doping Moyer, J. A.; Vaz, C. A. F.; Negusse, E. Physical Review B, Vol. 83, Issue 3 https://doi.org/10.1103/PhysRevB.83.035121	journal	January 2011
Composition, structure, and stability of ${RuO}_{2} (110)$ as a function of oxygen pressure Reuter, Karsten; Scheffler, Matthias Physical Review B, Vol. 65, Issue 3 https://doi.org/10.1103/PhysRevB.65.035406	journal	December 2001
Split-vacancy defect complexes of oxygen in hcp and fcc cobalt Honrao, Shreyas J.; Rizzardi, Quentin; Maaß, Robert Physical Review Materials, Vol. 4, Issue 10 https://doi.org/10.1103/PhysRevMaterials.4.103608	journal	October 2020
Intrinsic Activity of Oxygen Evolution Catalysts Probed at Single CoFe ₂ O ₄ Nanoparticles El Arrassi, Abdelilah; Liu, Zhibin; Evers, Mathies V. Journal of the American Chemical Society, Vol. 141, Issue 23 https://doi.org/10.1021/jacs.9b04516	journal	May 2019
Simple, Unambiguous Theoretical Approach to Oxidation State Determination via First-Principles Calculations Sit, Patrick H. -L.; Car, Roberto; Cohen, Morrel H. Inorganic Chemistry, Vol. 50, Issue 20 https://doi.org/10.1021/ic2013107	journal	October 2011
Structure of the NiFe2O4(001) surface in contact with gaseous O2 and water vapor Shi, Xiao; Li, Ye-Fei; Bernasek, Steve L. Surface Science, Vol. 640 https://doi.org/10.1016/j.susc.2015.03.012	journal	October 2015

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