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Title: Guiding Synthesis of Polymorphs of Materials Using Nanometric Phase Diagrams

Abstract

Conventionally, phase diagrams serve as road maps for the design and synthesis of materials. However, bulk phase diagrams are often not as predictive for the synthesis of nanometric materials, mainly due to the increased significance of surface energy. The change of surface energy can drastically alter the total energy of the nanocrystals and thus yields a polymorph or metastable phase different from the stable phase in bulk, providing a means for controlling the synthesis of metastable phases. To achieve a theoretical and systematical understanding on the polymorphism of nanomaterials, metallic cobalt was chosen as a model system, where the two polymorphs, fcc and hcp phases, can be tuned with 100% selectivity in a solvothermal reaction. Advanced in situ synchrotron X-ray diffraction (XRD) technique and density functional theory (DFT) calculationswere complementarily employed to reveal the size- and surface-dependent polymorphism at nanometer scale. The nanometric phase diagram provides a general predictive approach to guide the synthesis of metastable materials.

Authors:
 [1];  [2];  [2];  [3];  [4];  [3];  [2];  [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Univ. of Maryland, College Park, MD (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1483244
Alternate Identifier(s):
OSTI ID: 1489779
Report Number(s):
BNL-209475-2018-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
SC0012704; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 49; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Ma, Xuetian, Nolan, Adelaide M., Zhang, Shuo, Bai, Jianming, Xu, Wenqian, Wu, Lijun, Mo, Yifei, and Chen, Hailong. Guiding Synthesis of Polymorphs of Materials Using Nanometric Phase Diagrams. United States: N. p., 2018. Web. doi:10.1021/jacs.8b11029.
Ma, Xuetian, Nolan, Adelaide M., Zhang, Shuo, Bai, Jianming, Xu, Wenqian, Wu, Lijun, Mo, Yifei, & Chen, Hailong. Guiding Synthesis of Polymorphs of Materials Using Nanometric Phase Diagrams. United States. https://doi.org/10.1021/jacs.8b11029
Ma, Xuetian, Nolan, Adelaide M., Zhang, Shuo, Bai, Jianming, Xu, Wenqian, Wu, Lijun, Mo, Yifei, and Chen, Hailong. Tue . "Guiding Synthesis of Polymorphs of Materials Using Nanometric Phase Diagrams". United States. https://doi.org/10.1021/jacs.8b11029. https://www.osti.gov/servlets/purl/1483244.
@article{osti_1483244,
title = {Guiding Synthesis of Polymorphs of Materials Using Nanometric Phase Diagrams},
author = {Ma, Xuetian and Nolan, Adelaide M. and Zhang, Shuo and Bai, Jianming and Xu, Wenqian and Wu, Lijun and Mo, Yifei and Chen, Hailong},
abstractNote = {Conventionally, phase diagrams serve as road maps for the design and synthesis of materials. However, bulk phase diagrams are often not as predictive for the synthesis of nanometric materials, mainly due to the increased significance of surface energy. The change of surface energy can drastically alter the total energy of the nanocrystals and thus yields a polymorph or metastable phase different from the stable phase in bulk, providing a means for controlling the synthesis of metastable phases. To achieve a theoretical and systematical understanding on the polymorphism of nanomaterials, metallic cobalt was chosen as a model system, where the two polymorphs, fcc and hcp phases, can be tuned with 100% selectivity in a solvothermal reaction. Advanced in situ synchrotron X-ray diffraction (XRD) technique and density functional theory (DFT) calculationswere complementarily employed to reveal the size- and surface-dependent polymorphism at nanometer scale. The nanometric phase diagram provides a general predictive approach to guide the synthesis of metastable materials.},
doi = {10.1021/jacs.8b11029},
journal = {Journal of the American Chemical Society},
number = 49,
volume = 140,
place = {United States},
year = {2018},
month = {11}
}

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Works referenced in this record:

Size effects on the hydrogen storage properties of nanostructured metal hydrides: A review
journal, January 2007

  • Bérubé, Vincent; Radtke, Gregg; Dresselhaus, Mildred
  • International Journal of Energy Research, Vol. 31, Issue 6-7
  • DOI: 10.1002/er.1284

Magnetic Properties of Nanostructured Materials
journal, January 1996

  • Leslie-Pelecky, Diandra L.; Rieke, Reuben D.
  • Chemistry of Materials, Vol. 8, Issue 8
  • DOI: 10.1021/cm960077f

Optical properties and biomedical applications of plasmonic nanoparticles
journal, January 2010

  • Khlebtsov, Nikolai G.; Dykman, Lev A.
  • Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 111, Issue 1
  • DOI: 10.1016/j.jqsrt.2009.07.012

Particle Size Dependence of the Ionic Diffusivity
journal, October 2010

  • Malik, Rahul; Burch, Damian; Bazant, Martin
  • Nano Letters, Vol. 10, Issue 10
  • DOI: 10.1021/nl1023595

Technological innovation processes revisited
journal, November 2006


TiO 2 Stability Landscape:  Polymorphism, Surface Energy, and Bound Water Energetics
journal, December 2006

  • Levchenko, Andrey A.; Li, Guangshe; Boerio-Goates, Juliana
  • Chemistry of Materials, Vol. 18, Issue 26
  • DOI: 10.1021/cm061183c

Nucleation of metastable aragonite CaCO 3 in seawater
journal, March 2015

  • Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 11
  • DOI: 10.1073/pnas.1423898112

Understanding crystallization pathways leading to manganese oxide polymorph formation
journal, June 2018


Size-Controlled Growth of CdSe Nanocrystals in Microfluidic Reactors
journal, February 2003

  • Chan, Emory M.; Mathies, Richard A.; Alivisatos, A. Paul
  • Nano Letters, Vol. 3, Issue 2
  • DOI: 10.1021/nl0259481

Size-Controlled Synthesis of Magnetite Nanoparticles
journal, July 2002

  • Sun, Shouheng; Zeng, Hao
  • Journal of the American Chemical Society, Vol. 124, Issue 28
  • DOI: 10.1021/ja026501x

Synthesis of Silver Nanostructures with Controlled Shapes and Properties
journal, October 2007

  • Wiley, Benjamin; Sun, Yugang; Xia, Younan
  • Accounts of Chemical Research, Vol. 40, Issue 10
  • DOI: 10.1021/ar7000974

Shape control of CdSe nanocrystals
journal, March 2000

  • Peng, Xiaogang; Manna, Liberato; Yang, Weidong
  • Nature, Vol. 404, Issue 6773, p. 59-61
  • DOI: 10.1038/35003535

LiCoO 2 Concaved Cuboctahedrons from Symmetry-Controlled Topological Reactions
journal, January 2011

  • Chen, Hailong; Wu, Lijun; Zhang, Lihua
  • Journal of the American Chemical Society, Vol. 133, Issue 2
  • DOI: 10.1021/ja104852q

Citric Acid- and Ammonium-Mediated Morphological Transformations of Olivine LiFePO 4 Particles
journal, June 2011

  • Lu, Zhouguang; Chen, Hailong; Robert, Rosa
  • Chemistry of Materials, Vol. 23, Issue 11
  • DOI: 10.1021/cm200205n

Synthesis of Tin Dioxide Octahedral Nanoparticles with Exposed High-Energy {221} Facets and Enhanced Gas-Sensing Properties
journal, November 2009

  • Han, Xiguang; Jin, Mingshang; Xie, Shuifen
  • Angewandte Chemie International Edition, Vol. 48, Issue 48
  • DOI: 10.1002/anie.200903926

Molten Salt Synthesis and High Rate Performance of the “Desert-Rose” form of LiCoO2
journal, June 2008


Shape-Controlled Synthesis of Gold and Silver Nanoparticles
journal, December 2002


Synthesis, Optical Spectroscopy and Ultrafast Electron Dynamics of PbS Nanoparticles with Different Surface Capping
journal, November 2000

  • Patel, Amish A.; Wu, Fanxin; Zhang, Jin Z.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 49
  • DOI: 10.1021/jp000639p

MATERIALS SCIENCE: Nanocubes and Nanoboxes
journal, December 2002


Controlling the Shapes of Silver Nanocrystals with Different Capping Agents
journal, June 2010

  • Zeng, Jie; Zheng, Yiqun; Rycenga, Matthew
  • Journal of the American Chemical Society, Vol. 132, Issue 25
  • DOI: 10.1021/ja103655f

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
  • DOI: 10.1038/ncomms13799

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
  • DOI: 10.1021/jacs.6b11301

Revealing and Rationalizing the Rich Polytypism of Todorokite MnO 2
journal, April 2018

  • Hu, Xiaobing; Kitchaev, Daniil A.; Wu, Lijun
  • Journal of the American Chemical Society, Vol. 140, Issue 22
  • DOI: 10.1021/jacs.8b02971

Surface Phase Transitions during Martensitic Transformations of Single-Crystal Co
journal, September 1997


Magnetic Nanoparticles: Synthesis, Protection, Functionalization, and Application
journal, February 2007

  • Lu, An-Hui; Salabas, E. L.; Schüth, Ferdi
  • Angewandte Chemie International Edition, Vol. 46, Issue 8
  • DOI: 10.1002/anie.200602866

Microfluidic Synthesis of Cobalt Nanoparticles
journal, June 2006

  • Song, Yujun; Modrow, Hartwig; Henry, Laurence L.
  • Chemistry of Materials, Vol. 18, Issue 12
  • DOI: 10.1021/cm052811d

Gas phase synthesis of fcc-cobalt nanoparticles
journal, January 2006

  • Grass, Robert N.; Stark, Wendelin J.
  • Journal of Materials Chemistry, Vol. 16, Issue 19
  • DOI: 10.1039/b601013j

Fabrication of hcp-Co Nanocrystals via Rapid Pyrolysis in Inverse PS- b -PVP Micelles and Thermal Annealing
journal, July 2003

  • Diana, Frédéric S.; Lee, Seung-Heon; Petroff, Pierre M.
  • Nano Letters, Vol. 3, Issue 7
  • DOI: 10.1021/nl034262l

Synthesis of hcp-Co Nanodisks
journal, October 2002

  • Puntes, Victor F.; Zanchet, Daniela; Erdonmez, Can K.
  • Journal of the American Chemical Society, Vol. 124, Issue 43
  • DOI: 10.1021/ja027262g

Synthesis of cobalt nanoparticles in ethanol hydrazine alkaline system (EHAS) at room temperature
journal, November 2002


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A high-throughput infrastructure for density functional theory calculations
journal, June 2011


Li−Fe−P−O 2 Phase Diagram from First Principles Calculations
journal, February 2008

  • Ong, Shyue Ping; Wang, Lei; Kang, Byoungwoo
  • Chemistry of Materials, Vol. 20, Issue 5
  • DOI: 10.1021/cm702327g

EXPGUI , a graphical user interface for GSAS
journal, April 2001


Polyol-Mediated Synthesis of Nanoscale Functional Materials
journal, February 2003


Gibbs-Curie-Wulff Theorem in Organic Materials: A Case Study on the Relationship between Surface Energy and Crystal Growth
journal, December 2015


Shape Evolution of Cu 2 O Nanostructures via Kinetic and Thermodynamic Controlled Growth
journal, October 2006

  • Ng, Choon Hwee Bernard; Fan, Wai Yip
  • The Journal of Physical Chemistry B, Vol. 110, Issue 42
  • DOI: 10.1021/jp061835k

Size effect on the crystal phase of cobalt fine particles
journal, December 1997


Negative electrodes for Na-ion batteries
journal, January 2014

  • Dahbi, Mouad; Yabuuchi, Naoaki; Kubota, Kei
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 29
  • DOI: 10.1039/c4cp00826j

Recent developments in electrode materials for sodium-ion batteries
journal, January 2015

  • Wang, Luyuan Paul; Yu, Linghui; Wang, Xin
  • Journal of Materials Chemistry A, Vol. 3, Issue 18
  • DOI: 10.1039/C4TA06467D

Mechanism of acidity generation on sulfur-promoted metal oxides
journal, September 1986

  • Jin, Tuo; Yamaguchi, Tsutomu; Tanabe, Kozo
  • The Journal of Physical Chemistry, Vol. 90, Issue 20
  • DOI: 10.1021/j100411a017

Works referencing / citing this record:

Toward materials-by-design: achieving functional materials with physical and chemical effects
journal, October 2019