Crystal structures of lazulite-type oxidephosphates TiIIITiIV3O3(PO4)3 and MIII4TiIV27O24(PO4)24 (MIII=Ti, Cr, Fe)

Schöneborn, M.; Glaum, Robert; Reinauer, Felix

doi:10.1016/j.jssc.2008.02.039

Cited by 15 publications

(8 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Equilibrium experiments in the region (VO) 2 P 2 O 7 /VPO 4 /VO 2 of the V/P/O system provided the first evidence for a hitherto unknown vanadium phosphate . The X-ray powder diffraction pattern of the new phase showed strong resemblance to that of the mixed-valence titanium(III,IV) oxide phosphate Ti 4 O 3 (PO 4 ) 3 . − In the present paper we report on synthesis, crystallization, crystal structure, and catalytic behavior of the new vanadium(III,IV) oxide phosphate. It was of particular interest to our study to investigate the substitution of vanadium in V 4 O 3 (PO 4 ) 3 by other metals and to characterize the redox behavior of the oxide phosphate, the latter attribute being the key to understanding of the catalytic activity of vanadium phosphates in selective oxidation reactions of alkanes.…”

Section: Introductionmentioning

confidence: 76%

“…In addition to the introduction of octahedral voids into the structure of β-V 2 O(PO 4 ) 2 by oxidation of V 2+/3+ and/or substitution of O 2- by OH - and OH 2 the structure type shows even more crystal chemical flexibility. Thus, titanium oxide phosphates □ 3 Ti 5 O 4 (PO 4 ) 4 , Ti 31 O 24 (PO 4 ) 24 , and Ti 4 O 3 (PO 4 ) 3 with average oxidation states for titanium of +4.00, +3.87, and +3.75, respectively, have been characterized as members of the Lazulite/Lipscombite structure family, , with Ti 4 O 3 (PO 4 ) 3 being isotypic to □ 2 V 4 O 3 (PO 4 ) 3 . Interestingly, there exists apparently no counter part to □ 3 Ti 5 O 4 (PO 4 ) 4 with tetravalent vanadium (Figure ).…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

V^IIIV^IV₃O₃(PO₄)₃: A Novel Vanadium Phosphate for Selective Oxidation of Light Hydrocarbons

et al. 2007

View full text Add to dashboard Cite

A novel vanadium(IV) phosphate V III V IV 3 O 3 (PO 4 ) 3 has been synthesized and crystallized (1073 K, sealed silica tube, a few milligrams of PtCl 2 as mineralizer). According to the single-crystal structure analysis [orthorhombic, F2dd (No. 63), Z ) 24, a ) 7.2596(8) Å, b ) 21.786(2) Å, c ) 38.904(4) Å (lattice parameters from Guinier photographs), R 1 ) 0.032, wR 2 ) 0.067, κ-CCD diffractometer, 83 949 reflections measured, 6836 independent, 5986 with I > 2σ(I), 299 variables], V III V IV 3 O 3 (PO 4 ) 3 belongs to the Lipscombite/Lazulite structure family. At 1073 K V III V IV 3 O 3 (PO 4 ) 3 is in thermodynamic equilibrium with (VO) 2 P 2 O 7 , VO 2 , and VPO 4 . Substitution of V 3+ in V III V IV 3 O 3 (PO 4 ) 3 by Cr 3+ and Fe 3+ is possible. Like vanadylpyrophosphate the oxide phosphates M III V IV 3 O 3 (PO 4 ) 3 (M III : V, Cr, Fe) show significant catalytic activity in selective oxidation of n-butane and 1-butene to maleic acid anhydride.

show abstract

Section: Introductionmentioning

confidence: 76%

Section: Resultsmentioning

confidence: 99%

V^IIIV^IV₃O₃(PO₄)₃: A Novel Vanadium Phosphate for Selective Oxidation of Light Hydrocarbons

et al. 2007

View full text Add to dashboard Cite

show abstract

“…. [31][32][33][34][35] The orthorhombic phase V 4 O 3 (PO 4 ) 3 consists of infinite chains of face sharing VO 6 octahedra and PO 4 tetrahedra. The three dimensional structure is formed by perpendicular chains along a, b axis connected with common vertices of oxide ion and PO 4 tetrahedra (Figure 1b) …”

Section: Resultsmentioning

confidence: 99%

Reversible Li Insertion Studies on V₄O₃(PO₄)₃as High Energy Storage Material for Li-Ion Battery Applications

Satyanarayana¹,

Rao²,

Pralong³

et al. 2016

J. Electrochem. Soc.

View full text Add to dashboard Cite

Li-insertion studies were performed on V 4 O 3 (PO 4 ) 3 that belongs to the libscombite/lazulite family. Availability of multiple oxidation states and vacancies in crystal structure allows for the insertion of more than 7 lithium ions per formula unit. We will show that in the voltage window of 1-4 V vs. Li + /Li, 6.0 Li-ions could be inserted leading to a reversible capacity of 195 mAh/g at a C/5 rate. A structural transformation is observed from ex-situ XRD patterns after the insertion of 2 lithium at 2.4 V vs. Li + /Li, consistent with the available crystallographic sites in the structure. Interestingly we show that from this phase Li 2 V 4 O 3 (PO 4 ) 3 , further lithium insertion lead to an amorphous material but the structure is completely recovered on charge. Layered hexagonal transition metal oxides LiMO 2 (here, M = Co, Mn, Ni, Fe, Cr) have been extensively studied for commercial Li-ion secondary battery applications.1,2 The substitution of Ni and Mn in LiCoO 2 results in composition of LiNi 1/3 Mn 1/3 Co 1/3 O 2 is proven to be a promising cathode material.3-6 Spinel LiMn 2 O 4 has shown more interest due to less toxic nature of Mn, but lagged in the competition for next generation cheap energy storage device in presence of manganese dissolution in electrolyte and structural instability. 7,8 To make structurally and electrochemically stable spinel LiMn 2 O 4 , the manganese (Mn) ion substituted with Ti, Cr, Fe, Co, Ni, Al and Mg were explored. 7,9-13 Even though layered and spinel transition metal oxides are extensively studied for Li ion battery applications, there is an existence of crystal structural problems while on charging to higher voltage where the electrolyte is unstable due to evolution of oxygen from de-lithiated transition metal oxide framework. To address this problem, more research focus on lithium containing metal phosphate LiFePO 4 , LiMnPO 4 , Li 3 V 2 (PO 4 ) 3 etc.14-16 have been explored as thermally stable electrode materials. Indeed, the bonding of oxygen to phosphorous stabilize the structure from oxygen evolution, differently to layered transition metal oxides whereas oxygen evolution occurs at high charge voltages.17,18 But the energy obtained for these materials is low compared to metal oxide materials due to its high molecular weight. To compensate the energy density of metal polyanionic materials, the number of electrons transferred per unit formula has to increase through oxidation or reduction of transition metal ions vs. ExperimentalFor the synthesis route of V 4 O 3 (PO 4 ) 3 , we use the same route that was described by E. Benser and co-workers 32 in which stoichiometric amounts of homemade precursors VO 2 , VPO 4 , and (VO) 2 P 2 O 7 are placed in a carbon coated evacuated quart tube at 800• C for the period of five days.The X-ray diffraction pattern was recorded in the 2θ scale range of 10-120• , Cu Kα as X-ray source using BRUKER (D8) diffractometer and Co Kα as X-ray source using PAN analytical diffractometer. Rietveld refinement was carried out using FULLPROF so...

show abstract

“…For all transition metals, but technetium and osmium, anhydrous phosphates have been known and crystallographically characterized [1][2][3][4][5] for some years. Remarkably, The wide variability of oxidation states of the metal and of the P/M ratio observed for anhydrous rhenium phosphates appears to be particularly noteworthy (Re IV P 2 O 7 , [6] Re V 2 O 3 (P 2 O 7 ), [7] Re VI 2 O 3 (PO 4 ) 2 , [8] Re VII O 2 (PO 4 ) [9] ).…”

Section: Introductionmentioning

confidence: 99%

Osmium(IV) pyrophosphate: Synthesis, Crystallization, and Ligand‐Field Analysis of the [Os^IVO₆] Chromophore

Glaum

Rössel²,

Daniels³

et al. 2022

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

Dedicated to Professor Caroline Röhr on her anniversaryTwo polymorphs of burgundy-red OsP 2 O 7 , with cubic (ZrP 2 O 7 structure type, Z = 4, a = 7.8276(4) Å, 3 × 3 × 3 superstructure with a' = 3a = 23.484(2) Å) and triclinic symmetry (ruby-red crystals, single-crystal X-ray structure determination, GeP 2 O 7 structure type, P � 1 (no. 2), Z = 2, a = 4.8072(7) Å, b = 6.8993(13) Å, c = 8.050(1) Å, α = 91.82(2)°, β = 92.92(1)°, γ = 107.42(2)°, 98 parameters, R 1 = 0.045, wR 2 = 0.144, 3006 unique reflections with j F o j > 4σ(F o )) have been obtained reducing OsO 4 by phosphorus in sealed silica ampoules followed by subsequent chemical vapour transport. Reaction with the wall led to mixed Si IV /Os IV silicophosphates (Os 1À x Si x ) 3 [Si 2 O(PO 4 ) 6 ] {x = 0.84, pale orange, Si IV 3 [Si 2 O(PO 4 ) 6 ] structure type, R � 3, Z = 3, a = 7.893(1) Å, c = 24.409(5) Å, 59 parameters, R 1 = 0.058, wR 2 = 0.160, 1311 unique reflections with 1033 j F o j > 4σ(F o ); x = 0.47, orange, Ge IV 3 [Si 2 O(PO 4 ) 6 ] structure type, P � 31c, Z = 2, a = 7.9979(3) Å, c = 16.4625(5) Å, 59 parameters, R 1 = 0.040, wR 2 = 0.094, 902 unique reflections with 749 j F o j > 4σ(F o )}. Both structures were refined from single-crystal data. Above 25 K triclinic OsP 2 O 7 shows temperature independent paramagnetism with a strong temperature dependence of m=m B pointing to 3 T 1g as electronic ground state for Os 4 + (d 4 ) with strong spin-orbit coupling leading to J = 0 and the nonmagnetic ground state of the octahedral [Os IV O 6 ] chromophore.. Optical spectra of both polymorphs of OsP 2 O 7 show similar combinations of intense sharp and broad absorption bands typical for d n electronic systems systems with both, spin-orbit coupling and ligand field splitting, being strong. The observations are consistent with the ligand-field parameters Δ o = 20000 cm À 1 , B = 704 cm À 1 , and ζ = 3454 cm À 1 for the octahedral [Os IV O 6 ] chromophore.

show abstract

Crystal structures of lazulite-type oxidephosphates TiIIITiIV3O3(PO4)3 and MIII4TiIV27O24(PO4)24 (MIII=Ti, Cr, Fe)

Cited by 15 publications

References 37 publications

V^IIIV^IV₃O₃(PO₄)₃: A Novel Vanadium Phosphate for Selective Oxidation of Light Hydrocarbons

V^IIIV^IV₃O₃(PO₄)₃: A Novel Vanadium Phosphate for Selective Oxidation of Light Hydrocarbons

Reversible Li Insertion Studies on V₄O₃(PO₄)₃as High Energy Storage Material for Li-Ion Battery Applications

Osmium(IV) pyrophosphate: Synthesis, Crystallization, and Ligand‐Field Analysis of the [Os^IVO₆] Chromophore

Contact Info

Product

Resources

About

Crystal structures of lazulite-type oxidephosphates TiIIITiIV3O3(PO4)3 and MIII4TiIV27O24(PO4)24 (MIII=Ti, Cr, Fe)

Cited by 15 publications

References 37 publications

VIIIVIV3O3(PO4)3: A Novel Vanadium Phosphate for Selective Oxidation of Light Hydrocarbons

VIIIVIV3O3(PO4)3: A Novel Vanadium Phosphate for Selective Oxidation of Light Hydrocarbons

Reversible Li Insertion Studies on V4O3(PO4)3as High Energy Storage Material for Li-Ion Battery Applications

Osmium(IV) pyrophosphate: Synthesis, Crystallization, and Ligand‐Field Analysis of the [OsIVO6] Chromophore

Contact Info

Product

Resources

About

V^IIIV^IV₃O₃(PO₄)₃: A Novel Vanadium Phosphate for Selective Oxidation of Light Hydrocarbons

V^IIIV^IV₃O₃(PO₄)₃: A Novel Vanadium Phosphate for Selective Oxidation of Light Hydrocarbons

Reversible Li Insertion Studies on V₄O₃(PO₄)₃as High Energy Storage Material for Li-Ion Battery Applications

Osmium(IV) pyrophosphate: Synthesis, Crystallization, and Ligand‐Field Analysis of the [Os^IVO₆] Chromophore