Award Abstract # 1410169
Synthesis and Properties of Complex Crystalline and Glassy Metal Chalcogenides

NSF Org: DMR
Division Of Materials Research
Recipient: NORTHWESTERN UNIVERSITY
Initial Amendment Date: July 12, 2014
Latest Amendment Date: July 12, 2014
Award Number: 1410169
Award Instrument: Standard Grant
Program Manager: Birgit Schwenzer
bschwenz@nsf.gov
 (703)292-4771
DMR
 Division Of Materials Research
MPS
 Directorate for Mathematical and Physical Sciences
Start Date: August 15, 2014
End Date: July 31, 2017 (Estimated)
Total Intended Award Amount: $495,000.00
Total Awarded Amount to Date: $495,000.00
Funds Obligated to Date: FY 2014 = $495,000.00
History of Investigator:
  • Mercouri Kanatzidis (Principal Investigator)
    m-kanatzidis@northwestern.edu
Recipient Sponsored Research Office: Northwestern University
633 CLARK ST
EVANSTON
IL  US  60208-0001
(312)503-7955
Sponsor Congressional District: 09
Primary Place of Performance: Northwestern University
2145 Sheridan Road
Evanston
IL  US  60208-3113
Primary Place of Performance
Congressional District:
09
Unique Entity Identifier (UEI): EXZVPWZBLUE8
Parent UEI:
NSF Program(s): SOLID STATE & MATERIALS CHEMIS
Primary Program Source: 01001415DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s):
Program Element Code(s): 176200
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.049

ABSTRACT

Non-technical Summary
New materials impact not only the physical sciences but also economic growth. At a grassroots level, the solid state and materials chemistry community recognizes the grand challenge of developing rational materials discovery strategies and identifying materials that are transformative in our understanding of physicochemical properties and in technological progress. With support from the Solid State and Materials Chemistry Program in the Division of Materials Research, this project help address this challenge by developing the chemistry of metal chalcogenides. In this context, the research team is building a rational, science-driven foundation to extract maximum scientific and technological benefit. The primary goals of this projecct are to discover and characterize new types of metal chalcogenide compounds, and to understand their structures, chemical bonding and physical properties. If successful, new materials enabling new applications or enhancing the effectiveness of existing technological applications will emerge. The project employs molten salts as powerful reaction media in which to seek formation of new materials with unusual physical properties. The project contributes significantly to the training and teaching of graduate students in the field of solid state and materials chemistry and helps to create a future workforce that understands the importance of new materials as drivers for new phenomena and technologies.

Technical Summary
The primary goals of this research are to discover and characterize new types of metal chalcogenide compounds, and to understand their structures, chemical bonding and physical properties. The project employs salt flux syntheses to seek new materials with novel structure and compositions. Well-defined building blocks are present in the flux reactions and their formation is guided by tuning the flux composition and temperature, which controls Lewis basicity and redox potential. An important question in this synthesis program is whether, using intermediate temperatures, one can guide the fundamental reaction chemistry occurring in molten salts to suppress the formation of undesirable compounds and favor crystallization of new ones. The project is based on the general theme of structure-composition-property relationships with the following question being central: How does one develop the tools and concepts, both intellectual and experimental, to discover new functional materials. Focusing on the chalcogenide class the project has the following directions: (a) synthesis in polychalcogenide fluxes focusing on early transition and main group metals, mixed metal systems and also on thio and telluro-arsenate and antimonate chemistry; (b) synthesis using mixed chalcogenide fluxes incorporating oxide salts; (c) creation of novel glasses from the crystalline compounds and their phase change behavior and (d) dissolution studies of selected promising chalcogenide phases to assess their potential for processing into more useful forms. The project is expected to enrich the knowledge of unusual and diverse chalcometallate building blocks and role they play in creating new compounds. Experimental characterization tools to be employed include X-ray crystallography optical, infrared and Raman spectroscopy, scanning and transmission electron microscopy, differential thermal analysis and scanning calorimetry, and measurements of electrical conductivity as well as optical second harmonic generation.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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(Showing: 1 - 10 of 38)
Douvali, A. and Papaefstathiou, G. S. and Gullo, M. P. and Barbieri, A. and Tsipis, A. C. and Malliakas, C. D. and Kanatzidis, M. G. and Papadas, I. and Armatas, G. S. and Hatzidimitriou, A. G. and Lazarides, T. and Manos, M. J. "Alkaline Earth Metal Ion/Dihydroxy-Terephthalate MOFs: Structural Diversity and Unusual Luminescent Properties" Inorganic Chemistry , v.54 , 2015 , p.5813-5826 10.1021/acs.inorgchem.5b00539
Douvali, A.; Tsipis, A. C.; Eliseeva, S. V.; Petoud, S.; Papaefstathiou, G. S.; Malliakas, C. D.; Papadas, I.; Armatas, G. S.; Margiolaki, I.; Kanatzidis, M. G.; Lazarides, T.; Manos, M. J. "Turn-On Luminescence Sensing and Real-Time Detection of Traces of Water in Organic Solvents by a Flexible Metal-Organic Framework." Angewandte Chemie-International Edition , v.54 , 2015 , p.1651
Fang, L.; Iyer, R. G.; Tan, G. J.; West, D. J.; Zhang, S. B.; Kanatzidis, M. G. "The New Phase TI4Sb6Se10 Sn5Sb2Se14 : A Naturally Formed Semiconducting Heterostructure with Two-Dimensional Conductance." J. Am. Chem. Soc , v.136 , 2014 , p.11079
Fard, Z. H. and Islam, S. M. and Kanatzidis, M. G. "Porous Amorphous Chalcogenides as Selective Adsorbents for Heavy Metals" Chemistry of Materials , v.27 , 2015 , p.6189-6192 10.1021/acs.chemmater.5b02805
Fard, Z. H. and Malliakas, C. D. and Mertz, J. L. and Kanatzidis, M. G. "Direct Extraction of Ag+ and Hg2+ from Cyanide Complexes and Mode of Binding by the Layered K2MgSn2S6 (KMS-2)" Chemistry of Materials , v.27 , 2015 , p.1925-1928 10.1021/acs.chemmater.5b00374
Fard, Z. H.; Islam, S. M.; Kanatzidis, M. G. "Porous Amorphous Chalcogenides as Selective Adsorbents for Heavy Metals." Chemistry of Materials , v.27 , 2015 , p.6189
Fard, Z. H.; Malliakas, C. D.; Mertz, J. L.; Kanatzidis, M. G. "Direct Extraction of Ag+ and Hg2+ from Cyanide Complexes and Mode of Binding by the Layered K2MgSn2S6 (KMS-2)." Chemistry of Materials , v.27 , 2015 , p.1925
Haynes, A. S. and Banerjee, A. and Saouma, F. O. and Otieno, C. O. and Jang, J. I. and Kanatzidis, M. G. "Phase Transition, Conformational Exchange, and Nonlinear Optical Third Harmonic Generation of ACsP(2)Se(8) (A = K, Rb, Cs)" Chemistry of Materials , v.28 , 2016 , p.2374-2383 10.1021/acs.chemmater.6600551
Haynes, A. S. and Saouma, F. O. and Otieno, C. O. and Clark, D. J. and Shoemaker, D. P. and Jang, J. I. and Kanatzidis, M. G. "Phase-Change Behavior and Nonlinear Optical Second and Third Harmonic Generation of the One-Dimensional K(l-x)CsXPSe6 and Metastable beta-CsPSe6" Chemistry of Materials , v.27 , 2015 , p.1837-1846 10.1021/acs.chemmater.5b00065
Haynes, A. S. and Saouma, F. O. and Otieno, C. O. and Clark, D. J. and Shoemaker, D. P. and Jang, J. I. and Kanatzidis, M. G. "Phase-Change Behavior and Nonlinear Optical Second and Third Harmonic Generation of the One-Dimensional K(l-x)CsXPSe6 and Metastable beta-CsPSe6" Chemistry of Materials , v.27 , 2015 , p.1837-1846 10.1021/acs.chemmater.5b00065
Haynes, A. S.; Banerjee, A.; Saouma, F. O.; Otieno, C. O.; Jang, J. I.; Kanatzidis, M. G. "Phase Transition, Conformational Exchange, and Nonlinear Optical Third Harmonic Generation of ACsP2Se8 (A = K, Rb, Cs)." Chemistry of Materials , v.28 , 2016 , p.2374
(Showing: 1 - 10 of 38)

PROJECT OUTCOMES REPORT

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

In this project we have made several exciting discoveries of a fundamental nature regarding materials with exceptional properties and high performance in several technological areas with high potential impact in applications. We have reported new metal sulfide, selenide and telluride materials with very strong nonlinear optical activity, semiconductor properties, as well as materials with promising radiation detector properties and materials useful for environmental remediation.  We also discovered novel materials with excellent ion-exchange properties and unprecedented structures. Our research strategy was based on the premise that exploratory syntheses conducted at lower or medium temperatures (e.g. 200-600 degrees) were more likely to lead to new phases with complex compositions and structures. The strategy also resolved also revolved around the ability to characterize our new compounds in a broad variety of physical methods and chemical techniques to ensure that remarkable and unanticipated properties are found and properly understood. The results obtained during the duration of this project point to new scientific insights and exciting research directions to pursue in the future. Some of the new materials discovered may find technological applications. Furthermore, the scholarly activities associated with this grant contributed significantly to the advanced research training, education and career development of human resources. The project produced 25 published peer-reviewed papers.


Last Modified: 08/24/2017
Modified by: Mercouri G Kanatzidis

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