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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. Sat . "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 = {Sat Oct 01 00:00:00 EDT 2016},
month = {Sat Oct 01 00:00:00 EDT 2016}
}

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

Citation Metrics:
Cited by: 2works
Citation information provided by
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  • 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
  • A new cobalt titanium monophosphate has been prepared by low temperature method. It crystallizes with the Nasicon-type structure. The indexation of the X-ray diffraction pattern is consistent with the R{bar 3} or the R32 space groups. The atomic arrangement is a three-dimensional framework formed by PO{sub 4} tetrahedra sharing corners with TiO{sub 6} octahedra. Co{sup 2+} is located in half of the antiprism M(1) sites in a centered (R{bar 3}) or off-centered (R32) position. The optical, EPR and magnetic data can account for a pure ionic Co-O bond.
  • The optical (energy level scheme) and magnetic properties (paramagnetic susceptibility as a function of the temperature and g values) of the polycrystalline Co{sub 0.5}Ti{sub 2}(PO{sub 4}){sub 3} were simultaneously produced by use of a crystal field theory involving a set of F{sup k}, {zeta}, free ion, and B{sub q}{sup k} crystal field parameters. The crystal field parameters calculated from the structure are in fair agreement with the experimental ones and permit us to assign R32 as the space group of the crystal structure.