Sulfated and phosphated mesoporous Nb oxide in the benzylation of anisole and toluene by benzyl alcohol

Materials possessing the high acidities of sulfated zirconia and the diffusion properties of mesoporous oxides are predicted to have numerous applications in the petrochemical industry. Because of surface deactivation and loss of structure under highly acidic conditions, there are few examples of materials which meet these specifications. In this work, mesoporous Nb oxide was treated with 1 M sulfuric acid or phosphoric acid and evaluated for their catalytic activities in the benzylation of toluene or anisole with benzyl alcohol. Characterization by XRD, nitrogen adsorption/desorption, and TEM demonstrated that the mesostructure was surprisingly stable to acid treatment. Pyridine adsorption and infrared spectroscopy (IR) showed a mixture of Lewis and Bronsted sites before and after acid treatment. Titration with a series of indicators demonstrated that sulfated mesoporous Nb oxide possesses a pKa of -8.2 and 31.784 mmol/g acid sites, roughly 100 times stronger than either bulk phosphated or sulfated niobia, which both possess pKa values in the range of -3.0. The best catalytic results in this study were achieved when using mesoporous Nb oxide treated with sulfuric acid; the conversion of benzyl alcohol with anisole to the benzylation product was 100% in 30 min, which is 200 times faster than the bulk catalyst. The extremely high activity was rationalized by the high number of strong Br?nsted sites on the surface coupled with the superior diffusion properties of the mesoporous system.     

Fischer-Tropsch synthesis on anchored Co/Nb2O5/Al2O3 catalysts: the nature of the surface and the effect on chain growth

A series of Co/x%Nb2O5/Al2O3 catalysts were prepared by anchoring niobia on an Al2O3 support at different niobia concentrations. Characterization of the structure and nature of surface active sites was attempted in order to correlate the CO hydrogenation activity of these systems with those of the Co/Al2O3 and Co/Nb2O5 catalysts. The effect of the reduction temperature on the CO hydrogenation activity and selectivity was studied, showing that interaction of cobalt and niobia surface species favored the selectivity for hydrocarbon chain growth. However, this effect is less pronounced on the niobia-promoted Co/Al2O3 compared to Co/Nb2O5 catalysts. X-ray photoelectron spectroscopy (XPS) and diffuse reflectance spectroscopy (DRS) results on Co/x%Nb2O5/Al2O3 showed prevailing amounts of Co2+ and Co3+ after calcination and reduction at 573 K, while, after reduction at 773 K, besides metallic cobalt, the Co2+ species still remains in contact with alumina, even for higher niobia loading. It seems that during this process formation and destruction of new interfaces involving Co0-NbOx sites takes place. Results suggest that Co0, Co0-Co2+, and Co0-NbOx are the active sites at the surface. The relative abundance of Co2+ species affects greatly the performance of the catalysts. DRIFTS and selectivity results suggest that these sites might be responsible for the reaction chain growth and therefore for the drastic change in the selectivity of CH4 and C5+ hydrocarbons mainly on the Co/Nb2O5 catalyst. DRIFTS results on Co/Nb2O5/Al2O3 showed the formation of -C=C- and -CH3- besides CHxO species. With increasing reduction temperature, the -C=C- species disappear while -CH3- fragments increased markedly, suggesting the formation of increasing amounts of hydrocarbons with higher chain length.     

Interatomic distance measurement in solid-state NMR between a spin- 1/2 and a spin- 5/2 using a universal REAPDOR curve

A universal curve for the solid-state NMR REAPDOR experiment on an isolated spin-1/2-spin-5/2 pair is proposed that provides a simple means to measure their interatomic distance. REAPDOR data were obtained at three separate REAPDOR experiments using different values of the rotor spinning frequency. All points were fitted simultaneously to the universal formula without a need for full density matrix calculations. The 13C-17O distance of 2.45 A was measured between the C6 carbon and the 17O label in a tyrosine sample. The error of 8% in the dipolar coupling (Dfit = 278 Hz) is well within the 15% theoretical tolerance of this curve.     

硅酸钠与有机硅氧烷前驱体合成有机官能化硅基介孔材料

采用有机硅氧烷（RTES）与硅酸钠（Na2SiO3)共水解缩聚合成有机官能化的 MSU型硅基介孔材料，当前驱体中RTES和硅酸钠的摩尔比为0.1:0.9时合成了R－ MSU（R＝甲基，氨基）分子筛，通过现代分析技术证明有机官能团均进入材料骨架 。选用CH3－MSU合成体系，考察了合成温度、前驱体与模板剂摩尔比及前驱体中有 机硅氧烷含量等反应参数对材料织构性能的影响，发现通过简单地调节反应参数， 能较好地控制材料的结构和表面特性。     

Effect of Brønsted/Lewis Acid Ratio on Conversion of Sugars to 5‐Hydroxymethylfurfural over Mesoporous Nb and Nb‐W Oxides

A series of mesoporous Nb and Nb‐W oxides were employed as highly active solid acid catalysts for the conversion of glucose to 5‐hydroxymethylfurfural (HMF ). The results of solid state ³¹P MAS NMR spectroscopy with adsorbed trimethylphosphine as probe molecule show that the addition of W in niobium oxide increases the number of Brønsted acid sites and decreases the number of Lewis acid sites. The catalytic performance for Nb‐W oxides varied with the ratio of Brønsted to Lewis acid sites and high glucose conversion was observed over Nb₅W₅ and Nb₇W₃ oxides with high ratios of Brønsted to Lewis acid sites. All Nb‐W oxides show a relatively high selectivity of HMF , whereas no HMF forms over sulfuric acid due to its pure Brønsted acidity. The results indicate fast isomerization of glucose to fructose over Lewis acid sites followed by dehydration of fructose to HMF over Brønsted acid sites. Moreover, comparing to the reaction occurred in aqueous media, the 2‐butanol/H₂O system enhances the HMF selectivity and stabilizes the activity of the catalysts which gives the highest HMF selectivity of 52% over Nb₇W₃ oxide. The 2‐butanol/H₂O catalytic system can also be employed in conversion of sucrose, achieving HMF selectivity of 46% over Nb₅W₅ oxide.     

Multinuclear NMR investigations of the oxygen, water, and hydroxyl environments in sodium hexaniobate

Solid-state (1)H, (17)O MAS NMR, (1)H-(93)Nb TRAPDOR NMR, and (1)H double quantum 2D MAS NMR experiments were used to characterize the oxygen, water, and hydroxyl environments in the monoprotonated hexaniobate material, Na(7)[HNb(6)O(19)].15H(2)O. These solid-state NMR experiments demonstrate that the proton is located on the bridging oxygen of the [Nb(6)O(19)](8-) cluster. The solid-state NMR results also show that the NbOH protons are spatially isolated from similar protons, but undergo proton exchange with the water species located in the crystal lattice. On the basis of double quantum (1)H MAS NMR measurements, it was determined that the water species in the crystal lattice have restricted motional dynamics. Two-dimensional (1)H-(17)O MAS NMR correlation experiments show that these restricted waters are preferentially associated with the bridging oxygen. Solution (17)O NMR experiments show that the hydroxyl proton is also attached to the bridging oxygen for the compound in solution. In addition, solution (17)O NMR kinetic studies for the hexaniobate allowed the measurement of relative oxygen exchange rates between the bridging, terminal, and hydroxyl oxygen and the oxygen of the solvent as a function of pH and temperature. These NMR experiments are some of the first investigations into the proton location, oxygen and proton exchange processes, and water dynamics for a base stable polyoxoniobate material, and they provide insight into the chemistry and reactivity of these materials.     

Matrix isolation infrared spectroscopic and theoretical studies on the reactions of niobium and tantalum mono- and dioxides with methane

The reactions of niobium and tantalum monoxides and dioxides with methane have been investigated using matrix isolation infrared spectroscopic and theoretical calculations. The niobium and tantalum oxide molecules were prepared by laser evaporation of Nb(2)O(5) and Ta(2)O(5) bulk targets. The niobium monoxide molecule interacted with methane to form the ONb(CH(4)) complex, which was predicted to have C(3)(v)() symmetry with the metal atom coordinated to three hydrogen atoms of the methane molecule. The ONb(CH(4)) complex rearranged to the CH(3)Nb(O)H isomer upon 300 nm < lambda < 580 nm irradiation. The analogous OTa(CH(4)) complex was not observed, but the CH(3)Ta(O)H molecule was produced upon UV irradiation. The niobium and tantalum dioxide molecules reacted with methane to form the O(2)Nb(CH(4)) and O(2)Ta(CH(4)) complexes with C(s)() symmetry, which underwent photochemical rearrangement to the CH(3)Nb(O)OH and CH(3)Ta(O)OH isomers upon ultraviolet irradiation.     

Highly crystalline inverse opal transition metal oxides via a combined assembly of soft and hard chemistries

A combined assembly of soft and hard chemistries is employed to generate highly crystalline three-dimensionally ordered macroporous (3DOM) niobia (Nb2O5) and titania (TiO2) structures by colloidal crystal templating. Polystyrene spheres with sp2 hybridized carbon are used in a reverse-template infiltration technique based on the aqueous liquid phase deposition of the metal oxide in the interstitial spaces of a colloidal assembly. Heating under inert atmosphere as high as 900 degrees C converts the polymer into sturdy carbon that acts as a scaffold and keeps the macropores open while the oxides crystallize. Using X-ray diffraction it is demonstrated that for both oxides this approach leads to highly crystalline materials while heat treatments to lower temperatures commonly used for polymer colloidal templating, in particular for niobia, results in only weakly crystallized materials. Furthermore it is demonstrated that heat treatment directly to higher temperatures without generating the carbon scaffold leads to a collapse of the macrostructure. The approach should in principle be applicable to other 3DOM materials that require heat treatments to higher temperatures.     

Synthesis, characterization, and luminescence properties of the ternary europium complex covalently bonded to mesoporous SBA-15

A novel mesoporous SBA-15 type of hybrid material (phen-SBA-15) covalently bonded with 1,10-phenanthroline (phen) ligand was synthesized by co-condensation of tetraethoxysilane (TEOS) and the chelate ligand 5-[N,N-bis-3-(triethoxysilyl)propyl]ureyl-1,10-phenanthroline (phen-Si) in the presence of Pluronic P123 surfactant as a template. The preservation of the chelate ligand structure during the hydrothermal synthesis and the surfactant extraction process was confirmed by Fourier transform infrared (FTIR) and (29)Si MAS NMR spectroscopies. SBA-15 consisting of the highly luminescent ternary complex Eu(TTA)(3)phen (TTA = 2-thenoyltrifluoroacetone) covalently bonded to a silica-based network, which was designated as Eu(TTA)(3)phen-SBA-15, was obtained by introducing the Eu(TTA)(3).2H(2)O complex into the hybrid materials via a ligand exchange reaction. XRD, TEM, and N(2) adsorption measurements were employed to characterize the mesostructure of Eu(TTA)(3)phen-SBA-15. For comparison, SBA-15 doped with Eu(TTA)(3).2H(2)O and Eu(TTA)(3)phen complexes and SBA-15 covalently bonded with a binary europium complex with phen ligand were also synthesized, and were named SBA-15/Eu(TTA)(3), SBA-15/Eu(TTA)(3)phen, and Eu-phen-SBA-15, respectively. The detailed luminescence studies on all the materials showed that, compared with the doping sample SBA-15/Eu(TTA)(3)phen and binary europium complex functionalized sample Eu-phen-SBA-15, the Eu(TTA)(3)phen-SBA-15 mesoporous hybrid material exhibited higher luminescence intensity and emission quantum efficiency. Thermogravimetric analysis on Eu(TTA)(3)phen-SBA-15 demonstrated that the thermal stability of the lanthanide complex was evidently improved as it was covalently bonded to the mesoporous SBA-15 matrix.     

氧化钨介孔材料的制备与表征

以介孔二氧化硅(KIT-6)为硬模板, 硅钨酸为钨源, 用硬模板法制备WO3-SiO2复合材料, 再利用HF除去二氧化硅, 得到了介孔三氧化钨材料. 用X射线衍射(XRD)、能量扩散X射线(EDX)、高分辨透射电镜(HRTEM)、N2吸附-脱附等表征手段, 对制备复合材料的物料比、煅烧温度以及不同分散剂等条件进行了考察. 结果表明, 硅钨酸与硅介孔的物料比(m(WO3)/m(SiO2))在3:1到4:1之间, 在600-750 ℃下煅烧, 能制备结构较好的介孔氧化钨. 乙醇和蒸馏水为分散剂时, 用乙醇为分散剂所得的介孔WO3材料具有更高的比表面积和孔体积.     

The first observation of heteronuclear two-bond J-coupling in the solid state: crystal structure and solid-state NMR spectroscopy of Rb(4)(NbO)(2)(Si(8)O(21))

High-temperature, high-pressure hydrothermal synthesis of the title compound and its (93)Nb and (29)Si MAS NMR spectra are reported. The (29)Si MAS NMR spectrum shows four signals corresponding to the four distinct Si sites in the structure. Three signals show multiplet patterns which arise from (93)Nb(spin-(9)/(2))-(29)Si J-coupling. This is the first example of two-bond J-coupling between a quadrupolar nucleus and a spin-(1)/(2) nucleus in the solid state. A combination of (93)Nb and (29)Si solid-state NMR and X-ray diffraction data has provided a correlation between NMR interaction parameters and local structure. This work opens a new opportunity to examine the relationship between (2)J-coupling and structural parameters in the solid state.     

Characterization of active phosphorus surface sites at synthetic carbonate-free fluorapatite using single-pulse 1H, 31P, and 31P CP MAS NMR

The chemically active phosphorus surface sites defined as PO(x), PO(x)H, and PO(x)H2, where x = 1, 2, or 3, and the bulk phosphorus groups of PO4(3-) at synthetic carbonate-free fluorapatite (Ca5(PO4)3F) have been studied by means of single-pulse 1H,31P, and 31P CP MAS NMR. The changes in composition and relative amounts of each surface species are evaluated as a function of pH. By combining spectra from single-pulse 1H and 31P MAS NMR and data from 31P CP MAS NMR experiments at varying contact times in the range 0.2-3.0 ms, it has been possible to distinguish between resonance lines in the NMR spectra originating from active surface sites and bulk phosphorus groups and also to assign the peaks in the NMR spectra to the specific phosphorus species. In the 31P CP MAS NMR experiments, the spinning frequency was set to 4.2 kHz; in the single-pulse 1H MAS NMR experiments, the spinning frequency was 10 kHz. The 31P CP MAS NMR spectrum of fluorapatite at pH 5.9 showed one dominating resonance line at 2.9 ppm assigned to originate from PO4(3-) groups and two weaker shoulder peaks at 5.4 and 0.8 ppm which were assigned to the unprotonated PO(x) (PO, PO2-, and PO3(2-)) and protonated PO(x)H (PO2H and PO3H-) surface sites. At pH 12.7, the intensity of the peak representing unprotonated PO(x) surface sites has increased 1.7% relative to the bulk peak, while the intensity of the peaks of the protonated species PO(x)H have decreased 1.4% relative to the bulk peak. At pH 3.5, a resonance peak at -4.5 ppm has appeared in the 31P CP MAS NMR spectrum assigned to the surface species PO(x)H2 (PO3H2). The results from the 1H MAS and 31P CP MAS NMR measurements indicated that H+, OH-, and physisorbed H2O at the surface were released during the drying process at 200 degrees C.     

Solid-state 93Nb and 13C NMR investigations of half-sandwich niobium(I) and niobium(V) cyclopentadienyl complexes

Solid-state 93Nb and 13C NMR experiments, in combination with theoretical calculations of NMR tensors, and single-crystal and powder X-ray diffraction experiments, are applied for the comprehensive characterization of structure and dynamics in a series of organometallic niobium complexes. Half-sandwich niobium metallocenes of the forms Cp'Nb(I)(CO)4 and CpNb(V)Cl4 are investigated, where Cp = C5H5- and Cp' = C5H4R- with R = COMe, CO2Me, CO2Et, and COCH2Ph. Anisotropic quadrupolar and chemical shielding (CS) parameters are extracted from 93Nb MAS and static NMR spectra for seven different complexes. It is demonstrated that 93Nb NMR parameters are sensitive to changes in temperature and Cp' ring substitution in the Cp'Nb(I)(CO)4 complexes. There are dramatic differences in the 93Nb quadrupolar coupling constants (C(Q)) between the Nb(I) and Nb(V) complexes, with C(Q) between 1.0 and 12.0 MHz for Cp'Nb(CO)4 and C(Q) = 54.5 MHz for CpNbCl4. The quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) pulse sequence is applied to rapidly acquire, in a piecewise fashion, a high signal-to-noise ultra-wide-line 93Nb NMR spectrum of CpNbCl4, which has a breadth of ca. 400 kHz. Solid-state 93Nb and 13C NMR spectra and powder XRD data are used to identify a new metallocene adduct coordinated at the axial position of the metal site by a THF molecule: CpNb(V)Cl4.THF. 13C MAS and CP/MAS NMR experiments are used to assess the purity of samples, as well as for measuring carbon CS tensors and the rare instance of one-bond 93Nb, 13C J-coupling, 1J(93Nb,13C). Theoretically calculated CS and electric field gradient (EFG) tensors are utilized to determine relationships between tensor orientations, the principal components, and molecular structures.     

Sandia octahedral molecular sieves (SOMS): structural and property effects of charge-balancing the M(IV)-substituted (M = Ti, Zr) Niobate framework

Sandia octahedral molecular sieves (SOMS) is an isostructural, variable composition class of ion exchangers with the general formula Na(2)Nb(2-x)M(IV)(x)O (6-x)(OH)(x).H(2)O (M(IV) = Ti, Zr; x = 0.04-0.40) where up to 20% of the framework Nb(V) can be substituted with Ti(IV) or Zr(IV). This class of molecular sieves is easily converted to perovskite through low-temperature heat treatment (500-600 degrees C). This report provides a detailed account of how the charge imbalance of this Nb(V)-M(IV) substitution is compensated. X-ray powder diffraction with Rietveld refinement, infrared spectroscopy, thermogravimetric analysis, (23)Na MAS NMR, and (1)H MAS NMR were used to determine how the framework anionic charge is cation-balanced over a range of framework compositions. All spectroscopic evidence indicated a proton addition for each M(IV) substitution. Evidences for variable proton content included (1) increasing OH observed by (1)H MAS NMR with increasing M(IV) substitution, (2) increased infrared band broadening indicating increased H-bonding with increasing M(IV) substitution, (3) increased TGA weight loss (due to increased OH content) with increasing M(IV) substitution, (4) no variance in population on the sodium sites (indicated by Rietveld refinement) with variable composition, and (5) no change in the (23)Na MAS NMR spectra with variable composition. Also observed by infrared spectroscopy and (23)Na MAS NMR was increased disorder on the Nb(V)/M(IV) framework sites with increasing M(IV) substitution, evidenced by broadening of these spectral features. These spectroscopic studies, along with ion exchange experiments, also revealed the effect of the Nb(V)/M(IV) framework substitution on materials properties. Namely, the temperature of conversion to NaNb(1-x)M(IV)(x)O(3) (M = Ti, Zr) perovskite increased with increasing Ti in the framework and decreased with increasing Zr in the framework. This suggested that Ti stabilizes the SOMS framework and Zr destabilizes the SOMS framework. Finally, comparing ion exchange properties of a SOMS material with minimal (2%) Ti to a SOMS material with maximum (20%) Ti revealed the divalent cation selectivity of these materials which was reported previously is a function of the M(IV) substitution in the framework. A thorough investigation of this class of SOMS materials has revealed the importance of understanding the influence of heterovalent substitutions in microporous frameworks on material properties.     

12-Tungstophosphates I-mmobilized on Chemically Modified Mesoporous Silica SBA-15

A functionalized material. PW/SBA-15m, was prepared successfully in diluted H2SO4 aqueous solutions by immobilizing 12-tungstophosphates on chemically modified mesoporous silica SBA-15 and characterized by elemental analysis, FTIR, ^31p MAS NMR, XRD and TEM. The results indicate that the framework of SBA-15 and the Keggin structure of PW12O40^3- were retained, and that 23%-33% (mass fraction) of PW12O40^3- wasimmobilized; the PW12O40^3- anions were finely dispersed on the pore wall of SBA-15. Having been leached in ethanol at 60 ℃ for 7 h, the loss of PW12O40^3- anions was not found.     

Ionothermal synthesis, crystal structure and solid-state NMR spectroscopy of a new organically templated gallium oxalatophosphate: (H2TMPD)0.5[Ga3(C2O4)0.5(PO4)3] (TMPD=N,N,N',N'-tetramethyl-1,3-propanediamine)

A new organically templated gallium oxalatophosphate, (C7H20N2)0.5[Ga3(C2O4)0.5(PO4)3], has been synthesized by using a low-melting-point eutectic mixture of choline chloride and oxalic acid as a solvent and characterized by single-crystal X-ray diffraction, thermogravimetric analysis and solid-state NMR spectroscopy. It is the first example of ionothermal synthesis of organically templated metal oxalatophosphate. The structure contains double 6-ring units of the composition Ga6(PO4)6 which are connected by oxalate ligands and P-O-Ga bonds to form a 3-D framework. The charge-compensating organic ammonium cations which are disordered over two positions are located at the intersections of two types of 8-ring channels. 1H MAS and 13C CPMAS NMR studies confirm the presence of N,N,N',N'-tetramethyl-1,3-propanediammonium cation. The 71Ga and 31P MAS NMR spectra are also consistent with the crystal structure analysis results.     

Elucidation of the solution structure and water-exchange mechanism of paramagnetic [Fe(II)(edta)(H(2)O)](2-)

The lability and structural dynamics of [Fe(II)(edta)(H(2)O)](2-) (edta = ethylenediaminetetraacetate) in aqueous solution strongly depend on solvent interactions. To study the solution structure and water-exchange mechanism, (1)H, (13)C, and (17)O NMR techniques were applied. The water-exchange reaction was studied through the paramagnetic effect of the complex on the relaxation rate of the (17)O nucleus of the bulk water. In addition to variable-temperature experiments, high-pressure NMR techniques were applied to elucidate the intimate nature of the water-exchange mechanism. The water molecule in the seventh coordination site of the edta complex is strongly labilized, as shown by the water-exchange rate constant of (2.7 +/- 0.1) x 106 s(-1) at 298.2 K and ambient pressure. The activation parameters DeltaH(not equal), DeltaS(not equal), and DeltaV(not equal) were found to be 43.2 +/- 0.5 kJ mol(-1), +23 +/- 2 J K(-1) mol(-1), and +8.6 +/- 0.4 cm(3) mol(-1), respectively, in line with a dissociatively activated interchange (Id) mechanism. The scalar coupling constant (A/h) for the Fe(II)-O interaction was found to be 10.4 MHz, slightly larger than the value A/h = 9.4 MHz for this interaction in the hexa-aqua Fe(II) complex. The solution structure and dynamics of [Fe(II)(edta)(H(2)O)](2-) were clarified by (1)H and (13)C NMR experiments. The complex undergoes a Delta,Lambda-isomerization process with interconversion of in-plane (IP) and out-of-plane (OP) positions. Acetate scrambling was also found in an NMR study of the corresponding NO complex, [Fe(III)(edta)(NO(-))](2-).     

Molecular precursors for ferroelectric materials: synthesis and characterization of Bi2M2(mu-O)(sal)4(Hsal)4(OEt)2 and BiM4(mu-O)4(sal)4(Hsal)3(O(i)Pr)4 (sal = O2CC6H4O,Hsal = O2CC6H4OH) (M = Nb,Ta)

Reactions between triphenyl bismuth, salicylic acid, and niobium or tantalum ethoxide have been explored. Four new coordination complexes incorporating bismuth and the group 5 metals niobium or tantalum have been synthesized and characterized spectroscopically, by elemental analysis, and by single crystal X-ray diffraction. The new complexes are Bi(2)M(2)(mu-O)(sal)(4)(Hsal)(4)(OEt)(2) (1a, M = Nb; 1b, M = Ta) and BiM(4)(mu-O)(4)(sal)(4)(Hsal)(3)(O(i)Pr)(4) (sal = O(2)CC(6)H(4)-2-O, Hsal = O(2)CC(6)H(4)-2-OH) (2a, M = Nb; 2b, M = Ta). Complexes 1a and 1b are isomorphous, as are 2a and 2b. The thermal and hydrolytic decomposition of 1a has been explored by DT/TGA and powder X-ray diffraction, while scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) were used to characterize the morphology and composition of the oxides. The heterobimetallic molecules are completely converted to the amorphous bimetallic oxide by heating to 500 degrees C in air. Decomposition of 1a or 1b at 650 degrees C produces the metastable high temperature form of BiNbO(4) as the major crystalline oxide phase. Heating samples of 1a to 850 degrees C favors conversion of the materials to the low temperature phase as well as disproportionation into Bi(5)Nb(3)O(15) and Nb(2)O(5). Thermal decomposition of 1a and 1b produces porous oxides, while hydrolytic decomposition of the complexes has been shown to produce nanometer scale bimetallic oxide particles. The potential of the complexes to act as single-source precursors for ferroelectric materials is considered.     

Mesoporous titanium phosphate molecular sieves with ion-exchange capacity.

Novel open framework molecular sieves, titanium(IV) phosphates named, i.e., TCM-7 and -8 (Toyota Composite Materials, numbers 7 and 8), with new mesoporous cationic framework topologies obtained by using both cationic and anionic surfactants are reported. The (31)P MAS NMR, UV-visible absorption, and XANES data suggest the tetrahedral state of P and Ti, and stabilization of the tetrahedral state of Ti in TCM-7/8 is due to the incorporation of phosphorus (at Ti/P = 1:1) vis-à-vis the most stable octahedral state of Ti in the pure mesoporous TiO(2). Mesoporous TCM-7 and -8 show anion exchange capacity due to the framework phosphonium cation and cation exchange capacity due to defective P-OH groups. The high catalytic activity in the liquid-phase partial oxidation of cyclohexene with a dilute H(2)O(2) oxidant supports the tetrahedral coordination of Ti in these materials.     

Synthesis, structural characterization, and molecular modeling of dodecaniobate keggin chain materials

Four new isostructural one-dimensional dodecaniobate Keggin materials, Na12[Ti2O2][TNb12O40] x xH2O and Na10[Nb2O2][TNb12O40] x xH2O with T = (Si or Ge), have been synthesized hydrothermally using a Lindqvist-ion salt, Na7[Nb6O19H] x 15H2O, as the precursor. Their structure, consisting of chains of Keggin ions [TNb12O40]16- linked by [Ti2O2]4+ or [Nb2O2]6+ bridges, was solved ab initio from powder diffraction data. The location of the charge-balancing sodium atoms and the water molecules was further investigated by molecular simulations. These compounds were also characterized by IR and solid-state 1H, 29Si, and 23Na MAS NMR spectroscopies. The structural relationships between these and related phases based on similar Keggin ion building units are discussed.