Understanding crystallization pathways leading to manganese oxide polymorph formation
Abstract
Hydrothermal synthesis is challenging in metal oxide systems with diverse polymorphism, as reaction products are often sensitive to subtle variations in synthesis parameters. This sensitivity is rooted in the non-equilibrium nature of low-Temperature crystallization, where competition between different metastable phases can lead to complex multistage crystallization pathways. Here, we propose an ab initio framework to predict how particle size and solution composition influence polymorph stability during nucleation and growth. We validate this framework using in situ X-ray scattering, by monitoring how the hydrothermal synthesis of MnO2 proceeds through different crystallization pathways under varying solution potassium ion concentrations ([K+] = 0, 0.2, and 0.33 M). We find that our computed size-dependent phase diagrams qualitatively capture which metastable polymorphs appear, the order of their appearance, and their relative lifetimes. Our combined computational and experimental approach offers a rational and systematic paradigm for the aqueous synthesis of target metal oxides.
- Authors:
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); National Renewable Energy Laboratory (NREL), Golden, CO (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1457088
- Alternate Identifier(s):
- OSTI ID: 1461258; OSTI ID: 1462356; OSTI ID: 1506381
- Report Number(s):
- NREL/JA-5F00-71965
Journal ID: ISSN 2041-1723; 2553; PII: 4917
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515; AC36-08GO28308
- Resource Type:
- Published Article
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Name: Nature Communications Journal Volume: 9 Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; computational chemistry; materials chemistry; materials for energy and catalysis
Citation Formats
Chen, Bor-Rong, Sun, Wenhao, Kitchaev, Daniil A., Mangum, John S., Thampy, Vivek, Garten, Lauren M., Ginley, David S., Gorman, Brian P., Stone, Kevin H., Ceder, Gerbrand, Toney, Michael F., and Schelhas, Laura T. Understanding crystallization pathways leading to manganese oxide polymorph formation. United Kingdom: N. p., 2018.
Web. doi:10.1038/s41467-018-04917-y.
Chen, Bor-Rong, Sun, Wenhao, Kitchaev, Daniil A., Mangum, John S., Thampy, Vivek, Garten, Lauren M., Ginley, David S., Gorman, Brian P., Stone, Kevin H., Ceder, Gerbrand, Toney, Michael F., & Schelhas, Laura T. Understanding crystallization pathways leading to manganese oxide polymorph formation. United Kingdom. https://doi.org/10.1038/s41467-018-04917-y
Chen, Bor-Rong, Sun, Wenhao, Kitchaev, Daniil A., Mangum, John S., Thampy, Vivek, Garten, Lauren M., Ginley, David S., Gorman, Brian P., Stone, Kevin H., Ceder, Gerbrand, Toney, Michael F., and Schelhas, Laura T. Fri .
"Understanding crystallization pathways leading to manganese oxide polymorph formation". United Kingdom. https://doi.org/10.1038/s41467-018-04917-y.
@article{osti_1457088,
title = {Understanding crystallization pathways leading to manganese oxide polymorph formation},
author = {Chen, Bor-Rong and Sun, Wenhao and Kitchaev, Daniil A. and Mangum, John S. and Thampy, Vivek and Garten, Lauren M. and Ginley, David S. and Gorman, Brian P. and Stone, Kevin H. and Ceder, Gerbrand and Toney, Michael F. and Schelhas, Laura T.},
abstractNote = {Hydrothermal synthesis is challenging in metal oxide systems with diverse polymorphism, as reaction products are often sensitive to subtle variations in synthesis parameters. This sensitivity is rooted in the non-equilibrium nature of low-Temperature crystallization, where competition between different metastable phases can lead to complex multistage crystallization pathways. Here, we propose an ab initio framework to predict how particle size and solution composition influence polymorph stability during nucleation and growth. We validate this framework using in situ X-ray scattering, by monitoring how the hydrothermal synthesis of MnO2 proceeds through different crystallization pathways under varying solution potassium ion concentrations ([K+] = 0, 0.2, and 0.33 M). We find that our computed size-dependent phase diagrams qualitatively capture which metastable polymorphs appear, the order of their appearance, and their relative lifetimes. Our combined computational and experimental approach offers a rational and systematic paradigm for the aqueous synthesis of target metal oxides.},
doi = {10.1038/s41467-018-04917-y},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United Kingdom},
year = {Fri Jun 29 00:00:00 EDT 2018},
month = {Fri Jun 29 00:00:00 EDT 2018}
}
https://doi.org/10.1038/s41467-018-04917-y
Web of Science
Works referenced in this record:
Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states
journal, June 2012
- Persson, Kristin A.; Waldwick, Bryn; Lazic, Predrag
- Physical Review B, Vol. 85, Issue 23
Photochemical Water Oxidation by Crystalline Polymorphs of Manganese Oxides: Structural Requirements for Catalysis
journal, February 2013
- Robinson, David M.; Go, Yong Bok; Mui, Michelle
- Journal of the American Chemical Society, Vol. 135, Issue 9
Computational predictions of energy materials using density functional theory
journal, January 2016
- Jain, Anubhav; Shin, Yongwoo; Persson, Kristin A.
- Nature Reviews Materials, Vol. 1, Issue 1
In situ Synthesis of Mixed-Valent Manganese Oxide Nanocrystals: An In situ Synchrotron X-ray Diffraction Study
journal, March 2006
- Shen, Xiong-Fei; Ding, Yun-Shuang; Hanson, Jonathan C.
- Journal of the American Chemical Society, Vol. 128, Issue 14
Induction time of a polymorphic transformation
journal, January 2017
- Sun, Wenhao; Ceder, Gerbrand
- CrystEngComm, Vol. 19, Issue 31
In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways
journal, September 2014
- Nielsen, M. H.; Aloni, S.; De Yoreo, J. J.
- Science, Vol. 345, Issue 6201
The high-throughput highway to computational materials design
journal, February 2013
- Curtarolo, Stefano; Hart, Gus L. W.; Nardelli, Marco Buongiorno
- Nature Materials, Vol. 12, Issue 3
Controllable hydrothermal synthesis of manganese dioxide nanostructures: shape evolution, growth mechanism and electrochemical properties
journal, January 2012
- Duan, Xiaochuan; Yang, Jiaqin; Gao, Haiyan
- CrystEngComm, Vol. 14, Issue 12
Turning Down the Heat: Design and Mechanism in Solid-State Synthesis
journal, March 1993
- Stein, A.; Keller, S. W.; Mallouk, T. E.
- Science, Vol. 259, Issue 5101
Energetics of polymorphs in density functional theory
journal, January 2016
- Kitchaev, Daniil A.; Peng, Haowei; Liu, Yun
- Physical Review B, Vol. 93, Issue 4
Manganese oxide minerals: Crystal structures and economic and environmental significance
journal, March 1999
- Post, J. E.
- Proceedings of the National Academy of Sciences, Vol. 96, Issue 7
Melting of Submonolayer Krypton Films on Graphite
journal, October 1978
- Horn, P. M.; Birgeneau, R. J.; Heiney, P.
- Physical Review Letters, Vol. 41, Issue 14
A Universal Representation of the States of Chemical Matter Including Metastable Configurations in Phase Diagrams
journal, November 2011
- Jansen, Martin; Pentin, Ilya V.; Schön, J. Christian
- Angewandte Chemie International Edition, Vol. 51, Issue 1
Interpretation of some γ-MnO 2 diffraction patterns
journal, April 1959
- de Wolff, P. M.
- Acta Crystallographica, Vol. 12, Issue 4
Evaluating structure selection in the hydrothermal growth of FeS2 pyrite and marcasite
journal, December 2016
- Kitchaev, Daniil A.; Ceder, Gerbrand
- Nature Communications, Vol. 7, Issue 1
Nanophase Transition Metal Oxides Show Large Thermodynamically Driven Shifts in Oxidation-Reduction Equilibria
journal, October 2010
- Navrotsky, Alexandra; Ma, Chengcheng; Lilova, Kristina
- Science, Vol. 330, Issue 6001
Orientational order in xenon fluid monolayers on single crystals of exfoliated graphite
journal, December 1985
- Nagler, S. E.; Horn, P. M.; Rosenbaum, T. F.
- Physical Review B, Vol. 32, Issue 11
A versatile sample-environment cell for non-ambient X-ray scattering experiments
journal, July 2008
- Chupas, Peter J.; Chapman, Karena W.; Kurtz, Charles
- Journal of Applied Crystallography, Vol. 41, Issue 4
Manganese Minerals in Clays: A Review
journal, January 1980
- Chukhrov, F. V.
- Clays and Clay Minerals, Vol. 28, Issue 5
Strongly Constrained and Appropriately Normed Semilocal Density Functional
journal, July 2015
- Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P.
- Physical Review Letters, Vol. 115, Issue 3
Low-Pressure, Metastable Growth of Diamond and "Diamondlike" Phases
journal, August 1988
- Angus, J. C.; Hayman, C. C.
- Science, Vol. 241, Issue 4868
Experimental setup for in situ X-ray SAXS/WAXS/PDF studies of the formation and growth of nanoparticles in near- and supercritical fluids
journal, May 2010
- Becker, Jacob; Bremholm, Martin; Tyrsted, Christoffer
- Journal of Applied Crystallography, Vol. 43, Issue 4
Efficient creation and convergence of surface slabs
journal, November 2013
- Sun, Wenhao; Ceder, Gerbrand
- Surface Science, Vol. 617
Multiple pathways of crystal nucleation in an extremely supersaturated aqueous potassium dihydrogen phosphate (KDP) solution droplet
journal, October 2016
- Lee, Sooheyong; Wi, Haeng Sub; Jo, Wonhyuk
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 48
Nucleation and growth of magnetite from solution
journal, February 2013
- Baumgartner, Jens; Dey, Archan; Bomans, Paul H. H.
- Nature Materials, Vol. 12, Issue 4
Chimie Douce Approaches to the Synthesis of Metastable Oxide Materials
journal, July 1995
- Gopalakrishnan, J.
- Chemistry of Materials, Vol. 7, Issue 7
Vernadite is random-stacked birnessite: A discussion of the paper by F. V. Chukhrov et al.: ?Contributions to the mineralogy of authigenic manganese phases from marine manganese deposits? [Mineralium Deposita 14, 249?261 (1979)]
journal, July 1980
- Giovanoli, R.
- Mineralium Deposita, Vol. 15, Issue 2
Manganese oxide-based materials as electrochemical supercapacitor electrodes
journal, January 2011
- Wei, Weifeng; Cui, Xinwei; Chen, Weixing
- Chem. Soc. Rev., Vol. 40, Issue 3
Structural and electrochemical properties of the proton / γ-MnO2 system
journal, January 1995
- Chabre, Y.; Pannetier, J.
- Progress in Solid State Chemistry, Vol. 23, Issue 1
Quantification of Honeycomb Number-Type Stacking Faults: Application to Na 3 Ni 2 BiO 6 Cathodes for Na-Ion Batteries
journal, August 2016
- Liu, Jue; Yin, Liang; Wu, Lijun
- Inorganic Chemistry, Vol. 55, Issue 17
Comparison of the Photoelectronic and Photocatalytic Activities of Various Anatase and Rutile Forms of Titania in Pure Liquid Organic Phases and in Aqueous Solutions
journal, January 1996
- Sclafani, A.; Herrmann, J. M.
- The Journal of Physical Chemistry, Vol. 100, Issue 32
Thermodynamics of Phase Selection in MnO 2 Framework Structures through Alkali Intercalation and Hydration
journal, February 2017
- Kitchaev, Daniil A.; Dacek, Stephen T.; Sun, Wenhao
- Journal of the American Chemical Society, Vol. 139, Issue 7
Energetics of nanocrystalline TiO2
journal, March 2002
- Ranade, M. R.; Navrotsky, A.; Zhang, H. Z.
- Proceedings of the National Academy of Sciences, Vol. 99, Issue Supplement 2
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
High-fraction brookite films from amorphous precursors
journal, November 2017
- Haggerty, James E. S.; Schelhas, Laura T.; Kitchaev, Daniil A.
- Scientific Reports, Vol. 7, Issue 1
Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites
journal, June 2016
- Nagabhushana, G. P.; Shivaramaiah, Radha; Navrotsky, Alexandra
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 28
Polymorphous Transformations of Nanometric Iron(III) Oxide: A Review
journal, July 2011
- Machala, Libor; Tuček, Jiří; Zbořil, Radek
- Chemistry of Materials, Vol. 23, Issue 14
Surface Energies and Thermodynamic Phase Stability in Nanocrystalline Aluminas
journal, August 1997
- McHale, J. M.
- Science, Vol. 277, Issue 5327
Formation Mechanisms of Nanocrystalline MnO 2 Polymorphs under Hydrothermal Conditions
journal, January 2018
- Birgisson, Steinar; Saha, Dipankar; Iversen, Bo B.
- Crystal Growth & Design, Vol. 18, Issue 2
Selective heterogeneous oriented attachment of manganese oxide nanorods in water: toward 3D nanoarchitectures
journal, January 2009
- Portehault, David; Cassaignon, Sophie; Baudrin, Emmanuel
- Journal of Materials Chemistry, Vol. 19, Issue 42
Phase-controlled synthesis of polymorphic MnO 2 structures for electrochemical energy storage
journal, January 2015
- Yin, Bosi; Zhang, Siwen; Jiang, He
- Journal of Materials Chemistry A, Vol. 3, Issue 10
First Observation of Phase Transformation of All Four Fe 2 O 3 Phases (γ → ε → β → α-Phase)
journal, December 2009
- Sakurai, Shunsuke; Namai, Asuka; Hashimoto, Kazuhito
- Journal of the American Chemical Society, Vol. 131, Issue 51
The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese
journal, December 1971
- McKenzie, R. M.
- Mineralogical Magazine, Vol. 38, Issue 296
In situ studies of a platform for metastable inorganic crystal growth and materials discovery
journal, July 2014
- Shoemaker, D. P.; Hu, Y. -J.; Chung, D. Y.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 30
The influence of large cations on the electrochemical properties of tunnel-structured metal oxides
journal, November 2016
- Yuan, Yifei; Zhan, Chun; He, Kun
- Nature Communications, Vol. 7, Issue 1
Nonequilibrium models for predicting forms of precipitated manganese oxides
journal, November 1983
- Hem, John D.; Lind, Carol J.
- Geochimica et Cosmochimica Acta, Vol. 47, Issue 11
Porous Manganese Oxide Octahedral Molecular Sieves and Octahedral Layered Materials
journal, April 2008
- Suib, Steven L.
- Accounts of Chemical Research, Vol. 41, Issue 4
Nanoscale Effects on Thermodynamics and Phase Equilibria in Oxide Systems
journal, July 2011
- Navrotsky, Alexandra
- ChemPhysChem, Vol. 12, Issue 12
Particle Size Control and Self-Assembly Processes in Novel Colloids of Nanocrystalline Manganese Oxide
journal, September 1999
- Brock, Stephanie L.; Sanabria, Maria; Suib, Steven L.
- The Journal of Physical Chemistry B, Vol. 103, Issue 35
Crystal Structure Modeling of a Highly Disordered Potassium Birnessite
journal, January 1996
- Holland, Kerry L.
- Clays and Clay Minerals, Vol. 44, Issue 6
Multiphase transformation and Ostwald’s rule of stages during crystallization of a metal phosphate
journal, November 2008
- Chung, Sung-Yoon; Kim, Young-Min; Kim, Jin-Gyu
- Nature Physics, Vol. 5, Issue 1
The thermodynamic scale of inorganic crystalline metastability
journal, November 2016
- Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping
- Science Advances, Vol. 2, Issue 11