skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Accessing alkali-free NASICON-type compounds through mixed oxoanion sol–gel chemistry: Hydrogen titanium phosphate sulfate, H 1−x Ti 2 (PO 4 ) 3−x (SO 4 ) x ( x =0.5–1)

Authors:
; ;
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1399590
Grant/Contract Number:
SC0001016
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 242; Journal Issue: P2; Related Information: CHORUS Timestamp: 2017-10-14 01:45:40; Journal ID: ISSN 0022-4596
Publisher:
Elsevier
Country of Publication:
United States
Language:
English

Citation Formats

Mieritz, Daniel, Davidowski, Stephen K., and Seo, Dong-Kyun. Accessing alkali-free NASICON-type compounds through mixed oxoanion sol–gel chemistry: Hydrogen titanium phosphate sulfate, H 1−x Ti 2 (PO 4 ) 3−x (SO 4 ) x ( x =0.5–1). United States: N. p., 2016. Web. doi:10.1016/j.jssc.2016.02.007.
Mieritz, Daniel, Davidowski, Stephen K., & Seo, Dong-Kyun. Accessing alkali-free NASICON-type compounds through mixed oxoanion sol–gel chemistry: Hydrogen titanium phosphate sulfate, H 1−x Ti 2 (PO 4 ) 3−x (SO 4 ) x ( x =0.5–1). United States. doi:10.1016/j.jssc.2016.02.007.
Mieritz, Daniel, Davidowski, Stephen K., and Seo, Dong-Kyun. 2016. "Accessing alkali-free NASICON-type compounds through mixed oxoanion sol–gel chemistry: Hydrogen titanium phosphate sulfate, H 1−x Ti 2 (PO 4 ) 3−x (SO 4 ) x ( x =0.5–1)". United States. doi:10.1016/j.jssc.2016.02.007.
@article{osti_1399590,
title = {Accessing alkali-free NASICON-type compounds through mixed oxoanion sol–gel chemistry: Hydrogen titanium phosphate sulfate, H 1−x Ti 2 (PO 4 ) 3−x (SO 4 ) x ( x =0.5–1)},
author = {Mieritz, Daniel and Davidowski, Stephen K. and Seo, Dong-Kyun},
abstractNote = {},
doi = {10.1016/j.jssc.2016.02.007},
journal = {Journal of Solid State Chemistry},
number = P2,
volume = 242,
place = {United States},
year = 2016,
month =
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.jssc.2016.02.007

Save / Share:
  • We report a direct sol–gel synthesis and characterization of new proton-containing, rhombohedral NASICION-type titanium compounds with mixed phosphate and sulfate oxoanions. The synthetic conditions were established by utilizing peroxide ion as a decomposable and stabilizing ligand for titanyl ions in the presence of phosphates in a strong acidic medium. Thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), induction-coupled plasma optical emission spectroscopic (ICP-OES) elemental analysis, and Raman and {sup 1}H magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopic studies have determined the presence of sulfate and proton ions in the structure, for which the compositional range has been found to bemore » H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1). The particulate products exhibit a nanocrystalline nature observed through characterization with scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The N{sub 2} sorption isotherm measurements and subsequent Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) analyses confirmed the presence of the textural meso- and macropores in the materials. Future studies would determine the potential of the new compounds in various applications as battery materials, proton conductors and solid acid catalysts. - Graphical abstract: A series of proton-containing NASICON-type compounds, H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1), were discovered through a new sol–gel synthetic method that utilizes peroxide ion as a decomposable and stabilizing ligand for titanyl ions in the presence of phosphates in a strong acidic medium.« less
  • A new NASICON-related structure of lithium titanium phosphate Li{sub 2.72}Ti{sub 2}(PO{sub 4}){sub 3} has been determined. This compound crystallizes in an orthorhombic system, Pbcn, with a = 12.064 (3) {angstrom}, b = 8.663 (3) {angstrom}, c = 8.711 (4) {angstrom}, V = 910.4 (8) {angstrom}{sup 3}, and Z = 4. The single crystal structure of this novel mixed valent titanium(III/IV) phosphate reveals one titanium atom per asymmetric unit. Two lithium sites are characterized by a pair of distorted polyhedra, Li(1)O{sub 4} and Li(2)O{sub 5}, which share a common edge resulting in a short Li(1) . . . Li(2) distance, i.e.,more » 2.29 (5) {angstrom}. Magnetic susceptibility and microprobe analysis confirmed the structural composition. The room temperature ionic conductivity is comparable with that of the known Li{sub 1+x}Ti{sub 2{minus}x}{sup IV}In{sub x}{sup III}(PO{sub 4}){sub 3}, which suggests possible fast ionic conductivity.« less
  • The reaction of Np(V) chloride with molten boric acid results in the disproportionation of Np(V) into Np(IV) and Np(VI), and the crystallization of K{sub 2}[(NpO{sub 2}){sub 3}B{sub 10}O{sub 16}(OH){sub 2}(NO{sub 3}){sub 2}]. UV-vis-NIR spectroscopy demonstrates that in addition to the Np(VI) and Np(V) found in the crystal structure, Np(IV) is also present.