Reimagining the $e_g$1 Electronic State in Oxygen Evolution Catalysis: Oxidation-State-Modulated Superlattices as a New Type of Heterostructure for Maximizing Catalysis

Ding, Ran; Yasini, Parisa; Peng, Haowei; Perdew, John P.; Borguet, Eric; Zdilla, Michael J.

doi:10.1002/aenm.202101636

Reimagining the $$e_g$$¹ Electronic State in Oxygen Evolution Catalysis: Oxidation-State-Modulated Superlattices as a New Type of Heterostructure for Maximizing Catalysis

Journal Article · Fri Oct 01 00:00:00 EDT 2021 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202101636· OSTI ID:1976238

Ding, Ran ^[1]; Yasini, Parisa ^[2]; Peng, Haowei ^[2]; Perdew, John P. ^[2]; Borguet, Eric ^[2]; ^[2]

Temple University, Philadelphia, PA (United States); OSTI
Temple University, Philadelphia, PA (United States)

We report that the discovery of solid-phase, inexpensive transition-metal-based water oxidation catalysts is a central goal for renewable energy, and has led to a general consensus that a partially populated metal e_g d-electronic state is desirable, leading to favorable catalysis for certain elements in specific oxidation states. In manganese systems, the key species is manganese(III), whose high-spin d₄ electronic configuration places an unpaired electron in the e_g orbital, which is postulated to contribute to electronic and structural features that support catalysis. Based on density functional theory calculations, it is predicted that electron transfer would be facilitated by a catalyst with alternating low- and high-Mn^III-content sheets, which positions neighboring band edges in closer energetic proximity. The preparation of such catalysts is demonstrated for the first time and it is shown that the catalytic activity is maximized in these systems over more uniform, but more Mn^III-rich systems. The best catalyst possesses alternating high-and low-average oxidation state sheets with interlayer Cs⁺ ions, and has an overpotential of 450 mV at 10 mA, which represents an improvement of 250 mV over the best unmodified synthetic potassium birnessites. Using scanning tunneling spectroscopy, bandgap modulations consistent with the theoretically predicted band edge shifts are detected.

View Accepted Manuscript (DOE)

Research Organization:: Temple University, Philadelphia, PA (United States)

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

Grant/Contract Number:: SC0012575

OSTI ID:: 1976238

Alternate ID(s):: OSTI ID: 1823502

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 41 Vol. 11; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Large-Scale Exfoliation of Inorganic Layered Compounds in Aqueous Surfactant Solutions Smith, Ronan J.; King, Paul J.; Lotya, Mustafa Advanced Materials, Vol. 23, Issue 34 https://doi.org/10.1002/adma.201102584	journal	July 2011
Calcium Manganese(III) Oxides (CaMn ₂ O ₄ ⋅ x H ₂ O) as Biomimetic Oxygen-Evolving Catalysts Najafpour, Mohammad Mahdi; Ehrenberg, Till; Wiechen, Mathias Angewandte Chemie International Edition, Vol. 49, Issue 12 https://doi.org/10.1002/anie.200906745	journal	March 2010
Nickel Confined in the Interlayer Region of Birnessite: an Active Electrocatalyst for Water Oxidation Thenuwara, Akila C.; Cerkez, Elizabeth B.; Shumlas, Samantha L. Angewandte Chemie International Edition, Vol. 55, Issue 35 https://doi.org/10.1002/anie.201601935	journal	May 2016
Manganese Oxide as an Inorganic Catalyst for the Oxygen Evolution Reaction Studied by X‐Ray Photoelectron and Operando Raman Spectroscopy Radinger, Hannes; Connor, Paula; Stark, Robert ChemCatChem, Vol. 13, Issue 4 https://doi.org/10.1002/cctc.202001756	journal	December 2020
A mini review of NiFe-based materials as highly active oxygen evolution reaction electrocatalysts Gong, Ming; Dai, Hongjie Nano Research, Vol. 8, Issue 1 https://doi.org/10.1007/s12274-014-0591-z	journal	November 2014
XPS study of reductive dissolution of 7Å-birnessite by H3AsO3, with constraints on reaction mechanism Nesbitt, H. W.; Canning, G. W.; Bancroft, G. M. Geochimica et Cosmochimica Acta, Vol. 62, Issue 12 https://doi.org/10.1016/S0016-7037(98)00146-X	journal	June 1998
Effects of Co and Ni co-doping on the structure and reactivity of hexagonal birnessite Yin, Hui; Li, Hui; Wang, Yan Chemical Geology, Vol. 381 https://doi.org/10.1016/j.chemgeo.2014.05.017	journal	August 2014
Recent developments in electrochemical hydrogen evolution reaction Wang, Hao; Gao, Lijun Current Opinion in Electrochemistry, Vol. 7 https://doi.org/10.1016/j.coelec.2017.10.010	journal	January 2018
An Operando-Raman study on oxygen evolution of manganese oxides: Roles of phase composition and amorphization An, Hongyu; Chen, Zheng; Yang, Jingxiu Journal of Catalysis, Vol. 367 https://doi.org/10.1016/j.jcat.2018.08.007	journal	November 2018
Electrochemistry of Nanostructured Layered Transition-Metal Dichalcogenides Chia, Xinyi; Eng, Alex Yong Sheng; Ambrosi, Adriano Chemical Reviews, Vol. 115, Issue 21 https://doi.org/10.1021/acs.chemrev.5b00287	journal	October 2015
Geochemical Stability of Dissolved Mn(III) in the Presence of Pyrophosphate as a Model Ligand: Complexation and Disproportionation Qian, Ao; Zhang, Wen; Shi, Cheng Environmental Science & Technology, Vol. 53, Issue 10 https://doi.org/10.1021/acs.est.9b00498	journal	April 2019
Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis McKendry, Ian G.; Thenuwara, Akila C.; Shumlas, Samantha L. Inorganic Chemistry, Vol. 57, Issue 2 https://doi.org/10.1021/acs.inorgchem.7b01592	journal	October 2017
Birnessite: A Layered Manganese Oxide To Capture Sunlight for Water-Splitting Catalysis Lucht, Kevin P.; Mendoza-Cortes, Jose L. The Journal of Physical Chemistry C, Vol. 119, Issue 40 https://doi.org/10.1021/acs.jpcc.5b07860	journal	September 2015
Frustrated Solvation Structures Can Enhance Electron Transfer Rates Remsing, Richard C.; McKendry, Ian G.; Strongin, Daniel R. The Journal of Physical Chemistry Letters, Vol. 6, Issue 23 https://doi.org/10.1021/acs.jpclett.5b02277	journal	November 2015
Copper-Intercalated Birnessite as a Water Oxidation Catalyst Thenuwara, Akila C.; Shumlas, Samantha L.; Attanayake, Nuwan H. Langmuir, Vol. 31, Issue 46 https://doi.org/10.1021/acs.langmuir.5b02936	journal	November 2015
Tuning the Electrocatalytic Water Oxidation Properties of AB ₂ O ₄ Spinel Nanocrystals: A (Li, Mg, Zn) and B (Mn, Co) Site Variants of LiMn ₂ O ₄ Cady, Clyde W.; Gardner, Graeme; Maron, Zachary O. ACS Catalysis, Vol. 5, Issue 6 https://doi.org/10.1021/acscatal.5b00265	journal	May 2015
Coordination Geometry and Oxidation State Requirements of Corner-Sharing MnO ₆ Octahedra for Water Oxidation Catalysis: An Investigation of Manganite (γ-MnOOH) Smith, Paul F.; Deibert, Benjamin J.; Kaushik, Shivam ACS Catalysis, Vol. 6, Issue 3 https://doi.org/10.1021/acscatal.6b00099	journal	February 2016
Intercalation of Cobalt into the Interlayer of Birnessite Improves Oxygen Evolution Catalysis Thenuwara, Akila C.; Shumlas, Samantha L.; Attanayake, Nuwan H. ACS Catalysis, Vol. 6, Issue 11 https://doi.org/10.1021/acscatal.6b01980	journal	October 2016
Oxygen Evolution Activity on NiOOH Catalysts: Four-Coordinated Ni Cation as the Active Site and the Hydroperoxide Mechanism Li, Li-Fen; Li, Ye-Fei; Liu, Zhi-Pan ACS Catalysis, Vol. 10, Issue 4 https://doi.org/10.1021/acscatal.9b04975	journal	January 2020
Synergistic In-Layer Cobalt Doping and Interlayer Iron Intercalation into Layered MnO ₂ Produces an Efficient Water Oxidation Electrocatalyst McKendry, Ian G.; Mohamad, Loveyy J.; Thenuwara, Akila C. ACS Energy Letters, Vol. 3, Issue 9 https://doi.org/10.1021/acsenergylett.8b01217	journal	August 2018
Oxygen Vacancies and Intermediate Spin Trivalent Cobalt Ions in Lithium-Overstoichiometric LiCoO ₂ Levasseur, Stéphane; Ménétrier, Michel; Shao-Horn, Yang Chemistry of Materials, Vol. 15, Issue 1 https://doi.org/10.1021/cm021279g	journal	January 2003
Preparation of Layered MnO ₂ via Thermal Decomposition of KMnO ₄ and Its Electrochemical Characterizations Kim, Sa Heum; Kim, Sung Jin; Oh, Seung M. Chemistry of Materials, Vol. 11, Issue 3 https://doi.org/10.1021/cm9801643	journal	March 1999
Solar Water Splitting Cells Walter, Michael G.; Warren, Emily L.; McKone, James R. Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473 https://doi.org/10.1021/cr1002326	journal	November 2010
A Bifunctional Nonprecious Metal Catalyst for Oxygen Reduction and Water Oxidation Gorlin, Yelena; Jaramillo, Thomas F. Journal of the American Chemical Society, Vol. 132, Issue 39, p. 13612-13614 https://doi.org/10.1021/ja104587v	journal	October 2010
Photochemical Water Oxidation by Crystalline Polymorphs of Manganese Oxides: Structural Requirements for Catalysis Robinson, David M.; Go, Yong Bok; Mui, Michelle Journal of the American Chemical Society, Vol. 135, Issue 9 https://doi.org/10.1021/ja310286h	journal	February 2013
Effect of Interlayer Spacing on the Activity of Layered Manganese Oxide Bilayer Catalysts for the Oxygen Evolution Reaction Kang, Qing; Vernisse, Loranne; Remsing, Richard C. Journal of the American Chemical Society, Vol. 139, Issue 5 https://doi.org/10.1021/jacs.6b09184	journal	January 2017
A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes Yang, Jinhui; Cooper, Jason K.; Toma, Francesca M. Nature Materials, Vol. 16, Issue 3 https://doi.org/10.1038/nmat4794	journal	November 2016
Oxygen electrocatalysts in metal–air batteries: from aqueous to nonaqueous electrolytes Wang, Zhong-Li; Xu, Dan; Xu, Ji-Jing Chem. Soc. Rev., Vol. 43, Issue 22 https://doi.org/10.1039/C3CS60248F	journal	January 2014
Water-oxidation catalysis by synthetic manganese oxides – systematic variations of the calcium birnessite theme Frey, Carolin E.; Wiechen, Mathias; Kurz, Philipp Dalton Trans., Vol. 43, Issue 11 https://doi.org/10.1039/C3DT52604F	journal	January 2014
Decoration of the layered manganese oxide birnessite with Mn( ii / iii ) gives a new water oxidation catalyst with fifty-fold turnover number enhancement McKendry, Ian G.; Kondaveeti, Sandeep K.; Shumlas, Samantha L. Dalton Transactions, Vol. 44, Issue 29 https://doi.org/10.1039/C5DT01436K	journal	January 2015
Rapid determination of the Mn average oxidation state of Mn oxides with a novel two-step colorimetric method Zhu, Yanhua; Liang, Xinran; Zhao, Huaiyan Analytical Methods, Vol. 9, Issue 1 https://doi.org/10.1039/C6AY02472F	journal	January 2017
Insight into the effect of intercalated alkaline cations of layered manganese oxides on the oxygen reduction reaction and oxygen evolution reaction Kosasang, Soracha; Ma, Nattapol; Wuamprakhon, Phatsawit Chemical Communications, Vol. 54, Issue 62 https://doi.org/10.1039/C8CC03775B	journal	January 2018
Tuning the Lewis acidity of metal–organic frameworks for enhanced catalysis Devulapalli, Venkata Swaroopa Datta; Richard, Mélissandre; Luo, Tian-Yi Dalton Transactions, Vol. 50, Issue 9 https://doi.org/10.1039/D1DT00180A	journal	January 2021
Li₂MnO₃-stabilized LiMO₂ (M = Mn, Ni, Co) electrodes for lithium-ion batteries Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S. Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125 https://doi.org/10.1039/b702425h	journal	January 2007
Layered manganese oxides for water-oxidation: alkaline earth cations influence catalytic activity in a photosystem II-like fashion Wiechen, Mathias; Zaharieva, Ivelina; Dau, Holger Chemical Science, Vol. 3, Issue 7 https://doi.org/10.1039/c2sc20226c	journal	January 2012
Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation Birkner, N.; Nayeri, S.; Pashaei, B. Proceedings of the National Academy of Sciences, Vol. 110, Issue 22 https://doi.org/10.1073/pnas.1306623110	journal	May 2013
Importance of trivalency and the eg1 configuration in the photocatalytic oxidation of water by Mn and Co oxides Maitra, U.; Naidu, B. S.; Govindaraj, A. Proceedings of the National Academy of Sciences, Vol. 110, Issue 29 https://doi.org/10.1073/pnas.1310703110	journal	July 2013
Redox properties of birnessite from a defect perspective Peng, Haowei; McKendry, Ian G.; Ding, Ran Proceedings of the National Academy of Sciences, Vol. 114, Issue 36 https://doi.org/10.1073/pnas.1706836114	journal	August 2017
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
Calculation of multiplet structure of core p -vacancy levels Gupta, R. P.; Sen, S. K. Physical Review B, Vol. 10, Issue 1 https://doi.org/10.1103/PhysRevB.10.71	journal	July 1974
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
Liquid Exfoliation of Layered Materials Nicolosi, V.; Chhowalla, M.; Kanatzidis, M. G. Science, Vol. 340, Issue 6139, p. 1226419 https://doi.org/10.1126/science.1226419	journal	June 2013
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
The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese McKenzie, R. M. Mineralogical Magazine, Vol. 38, Issue 296 https://doi.org/10.1180/minmag.1971.038.296.12	journal	December 1971

Similar Records

Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis

Journal Article · Wed Jan 03 19:00:00 EST 2018 · Inorganic Chemistry · OSTI ID:1470025

Effect of water frustration on water oxidation catalysis in the nanoconfined interlayers of layered manganese oxides birnessite and buserite

Journal Article · Mon Feb 08 19:00:00 EST 2021 · Journal of Materials Chemistry. A · OSTI ID:1765589

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
catalysis
electrochemistry
layered materials
manganese oxides
oxygen evolution reaction
scanning tunneling spectroscopy
water oxidation

Reimagining the $$e_g$$1 Electronic State in Oxygen Evolution Catalysis: Oxidation-State-Modulated Superlattices as a New Type of Heterostructure for Maximizing Catalysis

Citation Formats

References (44)

Similar Records

Related Subjects

Reimagining the $$e_g$$¹ Electronic State in Oxygen Evolution Catalysis: Oxidation-State-Modulated Superlattices as a New Type of Heterostructure for Maximizing Catalysis