Tuning color through sulfur and fluorine substitutions in the defect tin(II, IV) niobate pyrochlores

Giampaoli, Gabriella; Li, Jun; Hermann, Raphael P.; Stalick, Judith K.; Subramanian, M. A.

doi:10.1016/j.solidstatesciences.2018.05.001

Title: Tuning color through sulfur and fluorine substitutions in the defect tin(II, IV) niobate pyrochlores

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Abstract

In this study, sulfur and fluorine substituted Sn₂Nb₂O₇ pyrochlore compounds were synthesized to produce brilliant orange/red colors as an environmentally friendly alternative to other toxic inorganic pigments. Neutron structure refinements indicate that the studied compositions crystallize in the pyrochlore structure with a large number of cation and/or anion vacancies and significant local structural disorder. The cubic unit cell decreases with increasing sulfur and fluorine content. The Sn²⁺ cation is off-center by 0.39–0.48 Å from the ideal site, and the oxygen O' is strongly displaced to the 32e position by an extraordinarily large distance that has never been reported for a pyrochlore type phase. The unprecedented displacive disorder and unusual lattice evolution upon sulfur substitution are presumably driven by the strong lone pair stereoactivity associated with Sn²⁺. Chemical analysis confirmed the existence of sulfur and fluorine, and ¹¹⁹Sn Mössbauer spectroscopy quantified the presence of both Sn²⁺ and Sn⁴⁺ in all compositions. The general formula representative of sulfur-containing pigments is nonstoichiometric Sn$$2+\atop{2-z}$$ (Nb_2-ySn$$4+\atop{y}$$)O_7-z-y/2-xS_x with the color varying according to x. The fluorine compound is refined to be Sn$$2+\atop{2}$$(Nb_0·958Ti_0.984Sn$$4+\atop{0.058}$$)O_6·376F_0.206 with exclusively anion vacancies. Optical characterization was performed through diffuse reflectance and color meter measurements. The band gap is determined to be in the range of 2.35 to 2.05 eV as sample color changes from yellow to orange/red. Finally, all powder samples show 60–95% reflectance in the near-infrared (NIR) region, adding new functionality to the application of these compounds as “cool” pigments.

Authors:

Giampaoli, Gabriella ^[1]; Li, Jun ^[1];

^[2]; Stalick, Judith K. ^[3]; Subramanian, M. A. ^[1]

Oregon State Univ., Corvallis, OR (United States). Department of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research

Publication Date:: Sat May 05 00:00:00 EDT 2018

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE

OSTI Identifier:: 1470895

Alternate Identifier(s):: OSTI ID: 1496390

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Solid State Sciences

Additional Journal Information:: Journal Volume: 81; Journal Issue: C; Journal ID: ISSN 1293-2558

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Defect pyrchlores; Anion substitutions; Neutron diffraction; Optical properties; Cool pigments

Citation Formats


                    Giampaoli, Gabriella, Li, Jun, Hermann, Raphael P., Stalick, Judith K., and Subramanian, M. A. Tuning color through sulfur and fluorine substitutions in the defect tin(II, IV) niobate pyrochlores.  United States: N. p., 2018. 
Web.  doi:10.1016/j.solidstatesciences.2018.05.001.

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                    Giampaoli, Gabriella, Li, Jun, Hermann, Raphael P., Stalick, Judith K., & Subramanian, M. A. Tuning color through sulfur and fluorine substitutions in the defect tin(II, IV) niobate pyrochlores.  United States.  https://doi.org/10.1016/j.solidstatesciences.2018.05.001

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                    Giampaoli, Gabriella, Li, Jun, Hermann, Raphael P., Stalick, Judith K., and Subramanian, M. A. Sat .  
"Tuning color through sulfur and fluorine substitutions in the defect tin(II, IV) niobate pyrochlores".  United States.  https://doi.org/10.1016/j.solidstatesciences.2018.05.001.  https://www.osti.gov/servlets/purl/1470895.

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@article{osti_1470895,

  title        = {Tuning color through sulfur and fluorine substitutions in the defect tin(II, IV) niobate pyrochlores},

  author       = {Giampaoli, Gabriella and Li, Jun and Hermann, Raphael P. and Stalick, Judith K. and Subramanian, M. A.},

  abstractNote = {In this study, sulfur and fluorine substituted Sn2Nb2O7 pyrochlore compounds were synthesized to produce brilliant orange/red colors as an environmentally friendly alternative to other toxic inorganic pigments. Neutron structure refinements indicate that the studied compositions crystallize in the pyrochlore structure with a large number of cation and/or anion vacancies and significant local structural disorder. The cubic unit cell decreases with increasing sulfur and fluorine content. The Sn2+ cation is off-center by 0.39–0.48 Å from the ideal site, and the oxygen O' is strongly displaced to the 32e position by an extraordinarily large distance that has never been reported for a pyrochlore type phase. The unprecedented displacive disorder and unusual lattice evolution upon sulfur substitution are presumably driven by the strong lone pair stereoactivity associated with Sn2+. Chemical analysis confirmed the existence of sulfur and fluorine, and 119Sn Mössbauer spectroscopy quantified the presence of both Sn2+ and Sn4+ in all compositions. The general formula representative of sulfur-containing pigments is nonstoichiometric Sn$2+\atop{2-z}$ (Nb2-ySn$4+\atop{y}$)O7-z-y/2-xSx with the color varying according to x. The fluorine compound is refined to be Sn$2+\atop{2}$(Nb0·958Ti0.984Sn$4+\atop{0.058}$)O6·376F0.206 with exclusively anion vacancies. Optical characterization was performed through diffuse reflectance and color meter measurements. The band gap is determined to be in the range of 2.35 to 2.05 eV as sample color changes from yellow to orange/red. Finally, all powder samples show 60–95% reflectance in the near-infrared (NIR) region, adding new functionality to the application of these compounds as “cool” pigments.},

  doi          = {10.1016/j.solidstatesciences.2018.05.001},

  journal      = {Solid State Sciences},

  number       = C,

  volume       = 81,

  place        = {United States},

  year         = {Sat May 05 00:00:00 EDT 2018},

  month        = {Sat May 05 00:00:00 EDT 2018}

}

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