0000000000898514
AUTHOR
J. Alamo
High temperature neutron diffraction study of sodium di-tin tri-phosphate
Abstract High temperature high resolution neutron diffraction study of the crystal chemistry of NaSn 2 (PO 4 ) 3 has been completed, at four different temperatures, applying the Rietveld method to the experimental neutron diffraction profile of a synthetic crystalline powder. Below the phase transition (∼860 K) the space group has been determined to be R3 which changes to R3c in the high temperature phase. No chemical bond breaks through the transition. The change in temperature makes the SnO 6 polyhedra rotate around the three fold axis in both structures. The PO 4 polyhedra rotate strictly around the two fold axis in the high temperature phase, but around the [0001] direction in the low t…
Vapor phase epitaxy of Hg1−xCdxI2 on sapphire
Abstract We demonstrate the possibility of growing Hg 1− x Cd x I 2 layers on sapphire substrates by vapor-phase epitaxy (VPE). The successful growth has been carried out using an α-HgI 2 polycrystalline source and a CdTe buffer layer grown on sapphire by metalorganic vapor phase epitaxy (MOVPE) before the Hg 1− x Cd x I 2 VPE growth. The Hg 1− x Cd x I 2 /sapphire 20–40 μm thick layers with a uniform composition in the range of x =0.2–0.6 were grown at 220–250°C for 70–300 h. The layers were studied by scanning electron microscopy, energy disperse X-ray analysis and X-ray diffractometry. Results on the layer characterization are reported and the effect of VPE conditions on the layer proper…
Stabilization of the rhombohedral phase in LiZr2(PO4)3 by thermal quenching
Abstract Two LiZr2(PO4)3 samples, which show rhombohedral and monoclinic symmetries, have been studied by powder XRD and MAS-NMR (31P and 7Li) techniques. In the monoclinic sample phosphorus occupies three crystallographic sites and lithium is preferentially placed in M2 environment. When the samples are subjected to successive heating-quenching treatments, the rhombohedral phase is not appreciably modified while the monoclinic phase is transformed into the rhombohedral one. In the quenched samples only one site for phosphorus has been detected and occupancy of lithium in the more symmetric M1 site is favoured. After the thermal treatments, when the samples are stored at room temperature fo…
Chemistry and properties of solids with the [NZP] skeleton
Abstract Solids with an [NZP] skeleton in their structure from a very broad family presenting very different properties with varying chemical composition. These properties range from radioactive nuclide immobilization and insulation to ionic and/or electronic conduction, extending to the field of very low thermal expansion among others. The open [NZP] skeleton provides the stability and flexibility necessary to form continuous ranges of solid solution, allowing the tailoring of the best composition-property-structure material. Chemical activity may become particularly high at the surface and absorption reactions and catalytic properties have the highest interest at present. In this paper, c…
Synthesis and Crystal Structure of a Novel Lamellar Barium Derivative: Ba(VOPO4)2·4H2O. Synthetic Pathways for Layered Oxovanadium Phosphate Hydrates M(VOPO4)2·nH2O
A unified synthetic strategy has allowed us to rationalize the preparative chemistry of the layered oxovanadium phosphates M(VOPO4)2·nH2O. Thus, we have been able to isolate as single phases with reasonable yields both all the previously characterized phosphates and a new solid containing Ba2+ cations as guest species as well as to prepare new related derivatives involving arsenate anions. In order to organize the experimental results, we have used two complementary models: a simple restatement of the partial charge model (PCM), and the valence matching principle (VMP) (derived from the bond valence method). The crystal structure of the new barium lamellar derivative, Ba(VOPO4)2·4H2O, has …
Interface charge density matching as driving force for new mesostructured oxovanadium phosphates with hexagonal structure, [CTA]xVOPO4·zH2O
Hexagonal mesostructured mixed-valence oxovanadium phosphates [CTA]xVOPO4·zH2O, in short ICMUV-2, have been synthesized through a S+I- cooperative mechanism using cationic surfactant (cetyltrimethylammonium, CTAB) rodlike micelles as a template. On the lines of the hypothesis that the driving force leading to the formation of mesostructured solids is the charge density matching at the interface between the supramolecular−organic and supramolecular−inorganic moieties, the self-assembling process between CTA+ micelles and VOPO4q- planar anions can be thought of as consequence of the adequate adjustment of the metal mean oxidation state. X-ray powder diffraction and TEM techniques show that th…
Ordered mesoporous materials: composition and topology control through chemistry
Abstract The atrane route constitutes a very versatile technique to obtain ordered mesoporous materials. A wide diversity of silica and silica-doped materials can be prepared by bringing into play fundamental synthesis parameters (like temperature, concentration and pH) which, in turn, allow modulation of the resulting material topology.
ChemInform Abstract: Chemistry and Properties of Solids with the (NZP) Skeleton
Abstract Solids with an [NZP] skeleton in their structure from a very broad family presenting very different properties with varying chemical composition. These properties range from radioactive nuclide immobilization and insulation to ionic and/or electronic conduction, extending to the field of very low thermal expansion among others. The open [NZP] skeleton provides the stability and flexibility necessary to form continuous ranges of solid solution, allowing the tailoring of the best composition-property-structure material. Chemical activity may become particularly high at the surface and absorption reactions and catalytic properties have the highest interest at present. In this paper, c…
Surfactant-Assisted Synthesis of Mesoporous Alumina Showing Continuously Adjustable Pore Sizes
Porous materials displaying tailor-made pore sizes and shapes are particularly interesting in a great variety of real and potential applications where molecular recognition is needed, such as shape-selective catalysis, molecular sieving, and selective adsorption. Classically, apart from silica, materials most commonly used for catalysis and catalyst supports have been those based on high surface aluminas, owing to their thermal, chemical, and mechanical stability and their low cost. Earlier aluminas with high surface areas (~500 m/g) had been prepared using structure-directing agents. However, they were X-ray amorphous materials and their porosity was purely textural, characterized by wide …
Supramolecular self-assembling in mesostructured materials through charge tuning in the inorganic phase
Supramolecular self-assembling of organic CTA+ micelles and inorganic [VO(H2O)PO4]n^q-2 2D-anions for the isolation of hexagonal mesostructured materials can be reached by charge tuning in the inorganic phase through the adjustment of the vanadium mean oxidation state. El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Cabrera Medina, Saul, Saul.Cabrera@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Alamo Serrano, Jaime, Jaime.Alamo@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es
Thermal expansion of LiZr2(PO4)3: Water inclusion influence
Abstract Lattice thermal expansion has been measured on three samples of composition LiZr 2 (PO 4 ) 3 , prepared by (i) a ceramic method, (ii) a gel-route and (iii) a nonstoichiometric ceramic. The first sample is monoclinic (?), with a transition at 50°C to rhombohedral. The second is clearly monoclinic with lattice parameters depending on the calcination temperature (700 to 1200°C. The third kind of synthesis yielded a new PO 4 -deficitary rhombohedral structure. X-ray diffraction measurements in a high temperature camera have been made from room temperature up to 1100°C. Lattice parameters, as well as their dependence on temperature are different for the three samples. While thermal expa…
Novel Phases in the V-P-O Catalytic System from Oxovanadium Hydrogenphosphate Precursors
ABSTRACTSeveral biphasic VOP04/(VO)2P2O7 redox partners seem to be active in the catalytic cycles involved in the mild oxidation of simple hydrocarbons to maleic anhydride. The present X-ray time resolved thermal-diffractometric study reveals the existence of a new anhydrous variety of the oxidized form, ω-VOPO4, which may appear as an intermediate in the formation of the well known β-VOPO4. This new phase only remains well crystallized at relatively high temperatures, and when it is allowed to cool down in wet air VOPO4·2H2O results. In turn, another well defined phase, VOPO4·1.58H2O, can be recognized in the course of the hydration process.
Design of ordered bimetallic complexes, Part 2:Trans-1,2-cyclohexanediaminetetraacetate bimetallates
Knowledge of the kinetic and thermodynamic behaviour of aqueous solutions containing two divalent cations andtrans-1,2-cyclohexanediaminetetraacetate has been used to design synthetic pathways to ordered bimetallic complexes
Phase transition in NaSn2(PO4)3 and thermal expansion of NaMIV2 (PO43; MIV = Ti, Sn, Zr
Abstract NaSn2(PO4)3 presents a fast and reversible second order phase transition about 575°C. Both phases above and below the transition point are rhombohedral. The high temperature phase is isostructural with NaTi2(PO4)3 and NaZr2(PO4)3, NZP structure. The lattice thermal expansion of these three compounds has been determined from x-ray diffraction data at different temperatures ranging from room temperature up to 1000°C. Differences in behaviour are discussed in relation to the structure.
Synthesis and structural study of sodium titanium phosphate-sodium tin phosphate solid solutions. II. Thermal expansion
Abstract The structure of NaTi 2 (PO 4 ) 3 shows the space group R3c, whereas that of NaSn 2 (PO 4 ) 3 presents the space group R3 at room temperature and it undergoes a second order phase transition at 575°C from this structure to another with the space group R3c. Evolution of the structure of NaTi 2 (PO 4 ) 3 NaSn 2 (PO 4 ) 3 solid solutions with temperature has been studied and temperature phase transition established for the compositions studied. Lattice thermal expansion of NaTi 2−x Sn x (PO 4 ) 3 solid solutions with x = 1, 1.2, 1.5 has been determined from x-ray diffraction data at temperatures ranging from 26 to 1000°C. DSC and dilatometric measurements have been also carried out o…
Structural study, thermal expansion and electrical conductivity of the composition NaSnZr(PO4)3
Abstract The structure of the composition NaSnZr(PO4)3 and its evolution with temperature has been studied. The structure presents the space group R 3 c. The refinement of the structure shows that the Sn and Zr atoms are statistically distributed over the same crystallographic position. The unit cell expands in the c direction and contracts in the a direction, remaining the space group R 3 c at temperatures between 26 and 1000°C. The low value of the electrical conductivity at 400°C, 5.729×10−7S/cm and the low density of the pellets limited the use as electrical conductor.
Prediction of Magnetic Properties in Oxovanadium(IV) Phosphates: The Role of the Bridging PO4 Anions
Oxovanadium phosphates constitute a crystallochemically very rich family that, in turn, results in a seemingly intricate magnetochemistry including from isolated dimers to 3-D systems. This magnetic diversity is due, in part, to the possible participation of phosphate groups in the spin transfer between VIV centers. This way, 31P solid-state NMR becomes a key tool in determining the exchange paths involving phosphorus orbitals. The magnetic behavior of several layered oxovanadium phosphates M(VOPO4)2·4H2O (M = Na+, Ca2+, Ba2+, and Pb2+) has been investigated. Like it occurs in the case of other previously studied lamellar derivatives, the best fit of the temperature-dependent magnetic susce…
Synthesis of a new mesostructured lamellar oxovanadium phosphate assembled through an S+X-I0 Mechanism
A new lamellar mesostructured oxovanadium(V) phosphate, (DDAH)0.9(Cl)0.9VOPO4·1.5H2O (DDA = dodecylamine), has been synthesized through a S+X-I0 cooperative mechanism using protonated dodecylamine ...
Crystal structure of a new polytype in the V–P–O system: is ω-VOPO4 a dynamically stabilised metastable network?
Abstract ω-VOPO 4 has been prepared by thermal decomposition of different oxovanadium hydrogen phosphates, namely VO(HPO 4 ) n H 2 O ( n =2( α ), 2(β) and 4) and β-NH 4 (VO 2 )(HPO 4 ). The ω-VOPO 4 phase only remains well crystallised at relatively high temperatures. Its crystal structure has been determined ab initio from X-ray powder diffraction data collected at 475°C. The cell is tetragonal (space group P4 2 /mmc) with a =4.8552(3) A and c =8.4301(6) A. Starting positional parameters were obtained by direct methods, and the structure was refined using Rietveld profile refinement principles. Disorder of two oxygen sublattices is observed. To rationalise some features of the crystal stru…
Synthesis and structural study of NaTi2(PO4)3-NaSn2(PO4)3 solid solutions. I. The effect of composition on lattice parameters
Abstract Compounds NaM2IV(PO4)3 with NZP-type structure present a different behavior depending on the nature of MIV. For MIV = Ti and Zr the structure shows the space group R3c, whereas for MIV = Sn the space group is R3. Differences in behavior of NaTi2(PO4)3 - NaSn2(PO4)3 solid solutions are discussed in relation to the composition. The variation of the lattice parameters with composition in NaTi2−xSnx(PO4)3 (0 1. The structure of the compound with x = 1 (NaSnTi(PO4)3) has been determined applying the Rietveld method to deconvolute the powder x-ray diffraction profile.
Preparation and structural study of sodium germanium phosphate-sodium titanium phosphate solid solutions. I. Evolution of structure with composition
Compounds NaM2IV(PO4)3 with M = Ge, Ti present the [NZP]-type structure, with a low thermal expansion. The space group at room temperature for the compound NaGe2(PO4)3 is R3, whereas for the compound NaTi2(PO4)3 is R3c. Evolution of the structure with composition in NaGe2(PO4)3 NaTi2(PO4)3 system is discussed. The space group and lattice parameters were determined for NaGe2−xTix(PO4)3 (0 < x < 2) solid solutions, prepared by ceramic method. Compositions rich in Ge(IV) (0 ≤ x ≤ 1) show the R3 space group, whereas for those rich in Ti(IV) (1.2 ≤ x ≤ 2) the space group is R3c. The variation of the lattice parameters with composition agreed with these results since it showed a change in its t…