Guiding Synthesis of Polymorphs of Materials Using Nanometric Phase Diagrams

doi:10.1021/jacs.8b11029

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

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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 thus yield a polymorph or meta-stable phase different than 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 functionals theory (DFT) were complementary employed to reveal the size and surface dependent polymorphism at nanometer scale. Furthermore, the nanometric phase diagram provides a general predictive approach to guide the synthesis of metastable materials.

Authors:

Ma, Xuetian ^[1]; Nolan, Adelaide M. ^[2]; Zhang, Shuo ^[2]; Bai, Jianming ^[3]; Xu, Wenqian ^[4]; Wu, Lijun ^[3]; Mo, Yifei ^[2]; Chen, Hailong ^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)
Univ. of Maryland, College Park, MD (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:: 2018-11-13

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) (SC-22)

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.

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                    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.  doi:10.1021/jacs.8b11029.

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                    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.  doi:10.1021/jacs.8b11029.  https://www.osti.gov/servlets/purl/1483244.

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@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 thus yield a polymorph or meta-stable phase different than 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 functionals theory (DFT) were complementary employed to reveal the size and surface dependent polymorphism at nanometer scale. Furthermore, 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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