Expanding the atrane route: Generalized surfactant-free synthesis of mesoporous nanoparticulated xerogels

Abstract A diversity of silica-based and non-silica nanoparticulated mesoporous xerogels have been synthesized from aqueous solution using a surfactant-free strategy, and starting from molecular atrane complexes as precursors. This approach constitutes an extension of the “atrane route” previously described for the surfactant-assisted synthesis of mesoporous materials, and allows us to unify the multiplicity of protocols described for the preparation of conventional xerogels. In fact, we have used exactly the same preparative conditions for obtaining all the compositions reported here. The xerogels synthesized in this way include pure silica (UVM-11), aluminosilicates and titanosilicates (M…

Mesoporous iron phosphate/phosphonate hybrid materials

Abstract Relatively high surface area pure mesoporous iron-phosphorus oxide-based derivatives have been synthesized through an S + I − surfactant-assisted cooperative mechanism by means of a one-pot preparative procedure from aqueous solution and starting from iron atrane complexes and phosphoric and phosphonic acids. A soft chemical extraction procedure allows opening the pore system of the parent as-prepared materials by exchanging the surfactant without mesostructure collapse. The nature of the pore wall can be modulated from iron phosphate up to hybrids involving approximately 30% of organophosphorus entities (phosphonates or diphosphonates). X-ray powder diffraction, transmission elect…

Pore Length Effect on Drug Uptake and Delivery by Mesoporous Silicas

The capability of UVM-7 silicas to work as supports for drug storage and delivery is investigated using ibuprofen as a model. UVM-7 silicas are surfactant-assisted synthesised mesoporous materials displaying a characteristic bimodal pore architecture related to their nanoparticulate texture. Strict control of the drug-charge protocol allows the achievement of high ibuprofen loads, not only because of the availability of intra-nanoparticle mesopores and large textural voids, but also owing to the decrease in pore-blocking effects (with regard to related unimodal mesoporous materials such as MCM-41) achieved through the shortening of the mesopore length. The UVM-7/ibuprofen nanocomposites are…

Enlarged pore size in nanoparticulated bimodal porous silicas: Improving accessibility

Abstract Mass-transfer kinetics seems to be highly favored in siliceous materials constructed from the aggregation of mesoporous nanoparticles. Besides intra-particle mesopores, over the course of the aggregation process an inter-particle (textural) large pore system is generated. Diffusion constrains through the resulting hierarchically structured pore systems mainly depend on the characteristics of the intra-particle mesopores. By using alkanes as swelling agents, we have been able to significantly increase the intra-particle mesopore size in previously well characterized UVM-7 materials. The Winsor-III-like behavior associated with the presence of alkanes in the hydro-alcoholic reaction …

Hierarchical porous carbon with designed pore architecture and study of its adsorptive properties

Abstract Ordered mesoporous carbon nanoparticles have been synthesized by a nanocasting procedure from furfuryl alcohol impregnation into alumino–silica UVM-7 material. By a proper adjustment of the synthesis parameters, furfuryl alcohol volume vs . template pore volume, it was possible to obtain a carbonaceous templated material which keeps the hierarchical bimodal porosity of the silica together with its high surface area (>1000 m 2 /g), as it was confirmed by means of electron transmission microscopy and N 2 adsorption isotherms. This carbon material was evaluated by testing it as a sorbent for several pesticides in aqueous solutions. Its absorption efficiency was compared with typical c…

One‐Pot Synthesis of a New High‐Aluminium‐Content Super‐Microporous Aluminosilicate

A new super-microporous aluminosilicate having a high aluminium content (Si/Al ca. 1) has been prepared through a surfactant-assisted procedure with the use of a commercially available binary precursor (di-sec-butoxyaluminooxytriethoxysilane) as a single source of both Al and Si. The formation of super-micropores is a result of a significant network shrinkage associated with the thermal elimination of the surfactant. This solid has been studied by X-ray powder diffraction, electron microscopy, nuclear magnetic resonance spectroscopy and porosimetry. A preliminary analysis of the acidity and the catalytic activity of the super-microporous solid for the selective catalytic reduction of NOx is…

Host Solids Containing Nanoscale Anion-Binding Pockets and Their Use in Selective Sensing Displacement Assays

ZnO nanoparticles embedded in UVM-7-like mesoporous silica materials: Synthesis and characterization

Abstract ZnO nanodomains embedded in bimodal mesoporous silica (UVM-7) materials with high Zn content (4≤Si/Zn≤30) have been synthesized by an one-pot surfactant-assisted procedure from a hydro alcoholic medium using a cationic surfactant (CTMABr=cetyltrimethylammonium bromide) as structural directing agent, and starting from molecular atrane complexes of Zn and Si as hydrolytic inorganic precursors. This chemical procedure allows optimizing the dispersion of the ZnO particles in the silica walls. The bimodal mesoporous nature of the final high surface area nano-sized materials is confirmed by XRD, TEM, and N2 adsorption–desorption isotherms. The small intra-particle mesopore system is due …

Large monolithic silica-based macrocellular foams with trimodal pore system.

Silica-based materials with hierarchical pore systems at three different length scales (small mesopores–large mesopores–macropores) have been prepared through a nanotectonic approach by using mesoporous nanoparticles as building blocks; the resulting materials present a highly accessible foam-like architecture and can be prepared as large monoliths. Huerta Morillo, Lenin Jose, Lenin.Huerta@uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Order and disorder in mixed metal linear chains: The homo and heterobimetallic EDTA (M(H2O)4OIOII)[M?(EDTA)] � 6H2O complexes (M = Mg, Mn, Co, Zn and Ni; M? = Co, Ni, Cu and Zn)

Polymetallic solid solutions of the ethylenediaminetetracetic acid (EDTA) and six divalent metal ions exist in the range: MgαMnβCoγZnδNieCuτ(EDTA) · 6H2O where α + β + γ + δ + e + τ=2, 0⩽τ⩽1, 0⩽γ,e,δ⩽2, 0⩽α, β⩽1. This type of structure is characterized by the presence of two different octahedral carboxylate-bridged coordination sites forming infinite zig-zag chains. Visible and i.r. spectra and t.g.a. analysis show that there is occupational preference for the two coordination sites in the crystalline structure. Due to this preference, and also to the structural features, the heterobimetallic MM′(EDTA) · 6H2O compounds constitute a structurally new class of materials which can be described …

Silica-based macrocellular foam monoliths with hierarchical trimodal pore systems

Abstract Silica-based large monoliths exhibiting a trimodal hierarchical pore system have been successfully prepared through a nanotectonic approach starting from sub-micro/nanometric mesoporous particles (as building blocks), and using a polyurethane foam as macrotemplate. Large trimodal pieces with macrocellular like interconnected macropores in the micrometer range are a mineralized replica of the polyurethane foam. Textural large-mesopores/macropores (in the 20–70 nm range) have their origin in the inter-particle voids. The small intra-particle mesopore system (with pore diameters around 2–3 nm) is due to the supramolecular templating effect of the surfactant.

Low Temperature Investigation of the Thermal and Magnetic Properties of 1-d Ferrimagnetic Systems

The series of structurally ordered bimetallic chains formulated as MM′ (EDTA).6H2O, in short (MM′), provides the most versatile known example of 1-dimensional ferrimagnets, since on the same structural support many different magnetic ions (Mn, Co, Ni and Cu(II)) can be selectively accommodated.1 Consequently, many choices of alternating magnetic moments with Heisenberg or Ising exchange couplings can be investigated. Moreover, taking into account that the M-M′ distances along the chain are alternating, this series could show at the same time an alternation of the exchange parameter2.

A novel ?-N-cyanate-bridged nickel dinier exhibiting ferromagnetic coupling: Di-?-cyanate-bis(aqua-2,2?:6?,2?-terpyridine)dinickel(II) hexafluorophosphate

AlTf-UVM-7—Highly active catalysts for the synthesis of long chain symmetrical ethers and non-ionic surfactant structures

New Lewis acid AlTf-UVM-7 catalysts with bimodal pore system and different Si to Al ratios were prepared in a two-step synthesis in which triflic acid (Tf) was incorporated into previously synthesized mesoporous aluminum-containing silica. The Al incorporation inside the pore walls was carried out through the Atrane method. The characterization of the resulted catalysts showed that the triflic acid treatment step did not damage the texture or the structure of the catalysts. These materials were used as green catalysts for the etherification of fatty alcohols and the conversion of ethylene glycol (EG) with n-octanol resulting in mixtures of short ethoxylated structures with a large distribut…

Improving epoxide production using Ti-UVM-7 porous nanosized catalysts

Nanosized Ti-UVM-7 materials with a hierarchical system of pores at two different length scales have been prepared through a one-pot procedure by using a simple template agent; the catalytic activity and selectivity of the resulting materials in bulky olefin epoxidation by organic peroxides are the highest reported to date.

Mesoporous aluminum phosphite

Abstract High surface area pure mesoporous aluminum-phosphorus oxide-based derivatives have been synthesized through an S+I− surfactant-assisted cooperative mechanism by means of a one-pot preparative procedure from aqueous solution and starting from aluminum atrane complexes and phosphoric and/or phosphorous acids. A soft chemical extraction procedure allows opening the pore system of the parent as-prepared materials by exchanging the surfactant without mesostructure collapse. The nature of the pore wall can be modulated from mesoporous aluminum phosphate (ALPO) up to total incorporation of phosphite entities (mesoporous aluminum phosphite), which results in a gradual evolution of the acid…

Nanoparticulated Silicas with Bimodal Porosity: Chemical Control of the Pore Sizes

Nanoparticulated bimodal porous silicas (NBSs) with pore systems structured at two length scales (meso- and large-meso-/macropores) have been prepared through a one-pot surfactant-assisted procedure by using a simple template agent and starting from silicon atrane complexes as hydrolytic inorganic precursors. The final bulk materials are constructed by an aggregation of pseudospherical mesoporous primary nanoparticles process, over the course of which the interparticle (textural) large pore system is generated. A fine-tuning of the procedural variables allows not only an adjustment of the processes of nucleation and growth of the primary nanoparticles but also a modulation of their subseque…

A new method for fluoride determination by using fluorophores and dyes anchored onto MCM-41Electronic supplementary information (ESI) available: IR spectra, SEM images, X-ray diffraction patterns and TG/TD analysis. See http://www.rsc.org/suppdata/cc/b1/b111128k/

A new colourimetric and fluorimetric method for fluoride determination in aqueous samples based on the specific reaction between fluoride and silica has been developed and applied on real samples.

Transport and Diamagnetic Properties of 2:2:1:2 and 2:2:2:3 (Bi-Pb)-Sr-Ca-Cu-O Superconducting Materials

AbstractBismuth superconducting oriented fibers of the compositions 2:2:1:2: and 2:2:2:3 have been grown by the Laser Floating Zone (LFZ) method. Growth conditions have been optimized in order to improve the superconducting properties. The 108 K onset in susceptibility measurements (associated to the 2:2:2:3 phase) only appears well defined when starting from Sr-defective precursors.

Magnetostructural correlations in parallel square-planar halo-bridged copper(II) dimers. Part II: Structure and magnetic properties of [Cu2(terpy)2Br2](PF6)2

Abstract The crystal and molecular structure of bis-μ- bromo-bis [(2,2′:6′,2″ - terpyridyl) copper (II) ] bis (hexafluorophosphate) has been determined from three dimensional single-crystal X-ray diffraction data, collected by counter techniques. The blue crystals belong to the monoclinic system, space group P21/a, with four formula units in a unit cell of dimensions a=20.40(2), b=13.35(2), c=6.453(8) A and β=97.74(9)°. The structure was solved using a refinement procedure and starting with the atomic positions of the isostructural complex [Cu(terpy)- Cl]2(PF6)2, to final agreement factors R=0.071 (Rw=0.077). The structure consists of dimeric molecules bridged by two bromine atoms. The coor…

Hierarchical bimodal porous silicas and organosilicas for enzyme immobilization

This work shows the ability of a hierarchical porous silica-based network with pore systems at two different length scales for enzyme immobilization. Two different enzymes have been selected, lysozyme, a relatively small globular enzyme, and α-L-arabinofuranosidase, a large enzyme of interest in the winemaking industry. The lysozyme immobilization on several silica supports (bimodal porous silicas denoted UVM-7 materials and conventional silica xerogels) has been studied and the loading amounts can be correlated to the open nature and accessibility of the internal surface area. Bimodal UVM-7 silicas present a very quick adsorption rate and high enzyme loading. α-L-Arabinofuranosidase has be…

Crystal structure, magnetic and spectroscopic properties of the bis(dimethyl sulfoxide) adduct of tetra-μ-formato-dicopper(II), a new tetracarboxylato-bridged copper(II) dimer

The crystal and molecular structure of a new tetracarboxylato-bridged copper(II) dimer, the bis(dimethyl sulfoxide)tetrakis(μ-formato)dicopper(II) has been determined by X-ray diffraction methods. It crystatlizes in the tetragonal space group I41/a, with Z=8 in a cell of dimensions a=17.688(2), c=10.408(1) Å. The structure is built up of centrosymmetric neutral dimers [Cu2(HCOO)4(dmso)2], where four bidentate carboxylate anions form syn-syn bridges between the metal atoms which are in a 4 + 1 environment. Magnetic susceptibility data show that the copper atoms are strongly antiferromagnetically coupled with J=-434 cm-1. The obtained triplet-singlet energy gap is compared with those reported…

The First Pure Mesoporous Aluminium Phosphonates and Diphosphonates − New Hybrid Porous Materials

Organophosphorus moieties have been incorporated into mesoporous ALPOs through a one-pot surfactant-assisted procedure leading, for the first time, to periodic mesoporous aluminium phosphonates and diphosphonates. The number of organic groups on the surface or in the network can be modulated continuously up to the maximum incorporation level of the respective organophosphorus entities (100 %). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

New heterogeneous catalysts for greener routes in the synthesis of fine chemicals

Abstract New strong Lewis acid SnTf-MCM-41 and SnTf-UVM-7 catalysts with unimodal and bimodal pore systems were prepared in a two-step synthesis in which the triflic acid (Tf) was incorporated to previously synthesized mesoporous tin-containing silicas. The Sn incorporation inside the pore walls was carried out through the Atrane method. The SnTf-UVM-7 catalysts were prepared by aggregating nanometric mesoporous particles defining a hierarchic textural-type additional pore system. Following these procedures, catalysts with different Si/Sn ratios—21.8 to 50.8 for SnTf-MCM-41 and 18.4 for SnTf-UVM-7—were prepared. These new materials were tested in the acylation of aromatic sulfonamides using…

Ferrimagnetic Heisenberg chain; influence of a random exchange interaction

We report on the magnetic behavior of ‘‘rigid’’ ferrimagnetic chains isolated in bimetallic complexes of the EDTA and ‘‘flexible’’ ones obtained in the amorphous variety. As shown by LAXS, the only noteworthy difference in the amorphous state is the random distribution of bond angles between nearest neighbors within chains. The ‘‘rigid’’ bimetallic chains in CoNi(EDTA)6H2O are described in terms of Heisenberg model with an exchange coupling J=−7.5 K. The behavior of the amorphous variety somewhat differs, following the law X=AT−0.8 typical of REHAC. A classical spin chain model involving a J distribution and alternating g factors allows to explain successfully the temperature dependence of …

New tubular transition metal oxoanionic derivatives: a systematic approach to condensed phases of the dumortierite family

Abstract An unified synthetic approach has allowed us to isolate a wide set of highly condensed oxoanionic derivatives of transition metals by using solution chemistry procedures. New phases are described [Ni 12+ x H 6−2 x (AsO 4 ) 8 (OH) 6 . Ni 6 (SeO 3 ) 4 (OH) 4 ], and the preparation of other already known [Ni 12+ x H 6−2 x (PO 4 ) 8 (OH) 6 , Ni 3 Te 2 O 6 (OH) 2 ] is significantly simplifi ed. The structure of these derivatives, as well as that of other phases such as M 11 (HPO 3 ) 8 (OH) 6 (M=Zn, Co, Ni), previously characterized by us, can be related to that of the dumortierite mineral. The main features of the tubular channels that characterize this structure and the possibility to …

Layered-Expanded Mesostructured Silicas: Generalized Synthesis and Functionalization

Mesostructured layered silicas have been prepared through a surfactant-assisted procedure using neutral alkylamines as templates and starting from atrane complexes as hydrolytic inorganic precursors. By adjusting the synthetic parameters, this kinetically controlled reproducible one-pot method allows for obtaining both pure and functionalized (inorganic or organically) lamellar silica frameworks. These are easily deconstructed and built up again, which provides a simple way for expanding the interlamellar space. The materials present high dispersibility, which results in stable colloidal suspensions.

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 …

(Bi,Pb)2Sr2Ca2Cu3O10+δ superconductor composites: Ceramics vs. fibers

Abstract Well characterized (Bi, Pb) 2 Sr 2 Ca 2 Cu 3 O 10+δ superconductor powder has been used to prepare superconductor-glass, -metal and -alloy composites through solid state reaction method. A recently developed Laser Floating Zone (LFZ) apparatus has been used to transform the ceramic precursors into oriented fibers. The diamagnetic properties have been studied by a.c. susceptibility. The microstructure of fibers has been studied by SEM and compared with that of the original ceramic precursors. XRD has been used to study phase composition on representative composite samples and fibers. The results indicate some potential for the 2223-Ag composite, which displays improved diamagnetic p…

Stable anchoring of dispersed gold nanoparticles on hierarchic porous silica-based materials

The nanometric organization of MOx (M = Co, Zn, Ni) domains partially embedded inside the mesoporous silica walls but accessible to the pore voids, which is achieved through a simple one-pot surfactant-assisted procedure, define optimal anchors for the nucleation and growth of gold nanoparticles, which in turn favours an exceptional thermal stability for the final Au-supported materials. As silica support we have selected a UVM-7 silica having a highly accessible architecture defined by two hierarchic pore systems. The combination of nanometric pore length, tortuous mesopores and MOx inorganic anchors favours the stability of the final Au/CoOx-UVM-7 nanocomposites.

Silica-based powders and monoliths with bimodal pore systemsElectronic supplementary information (ESI) available: UV–Vis spectrum of sample 3. See http://www.rsc.org/suppdata/cc/b1/b110883b/

Porous pure and doped silicas with pore sizes at two length scales (meso/macroporous) have been prepared and shaped both as powders and monoliths through a one-pot surfactant assisted procedure by using a simple template agent and starting from atrane complexes as inorganic precursors.

Design of Low-Dimensional Ferrimagnetic Compounds: New Magnetic Lattices in the “EDTA-Family”

The ability of EDTA to wrap around one metal atom (M′) while still providing bridging carboxylate groups to a second atom (M) is the basis for the obtainment of a wide variety of low-dimensional bimetallic ordered systems.

Efficient Sc triflate mesoporous-based catalysts for the synthesis of 4,4′-methylenedianiline from aniline and 4-aminobenzylalcohol

Abstract Sc triflate mesoporous-based catalysts have been prepared using a two-step strategy (i.e., Atrane method) based on the formation of the hierarchic bimodal porosity in the first step and the formation of Sc triflate complexes at the materials surface in the second step. All solids were analyzed by EPMA, surface area, and pore size values, XRD, TEM, FTIR, and 45Sc NMR static spectra. The catalysts have been investigated in the synthesis of 4,4′-methylenedianiline (4,4′-MDA) from aniline and 4-aminobenzylalcohol. 4,4′-MDA was obtained with selectivities over 85.0% for a conversion of aniline of 31%, at 80 °C and after 24 h. Using microwaves, selectivities of 90% in 4,4′-MDA were reach…

Kineticversus thermodynamic synthesis pathways of solid bimetallic coordination compounds ? Synthesis and crystal structure of some bimetallic compounds of glycineN,N?-1,2-cyclohexanedylbis[N-(carboxymethyl)]

Nano-sized mesoporous carbon particles with bimodal pore system and semi-crystalline porous walls

Acetylene CVD carbon replication of a hierarchical pore silica-based material, Fe-UVM-7, is reported. The original template organization, which is based on the aggregation of mesoporous nanoparticles, is accurately replicated in the final carbon material: a bimodal porous carbon combining mesoporous nanoparticles and inter-particle textural-like pores which provide high surface area, a highly accessible pore system and semi-crystalline pore walls in the form of graphitic-like nanodomains is presented.

High‐Zirconium‐Content Nano‐Sized Bimodal Mesoporous Silicas

Silica-based nanoparticulated bimodal mesoporous materials with high Zr content (43 ≥ Si/Zr ≥ 4) have been synthesized by a one-pot surfactant-assisted procedure from a hydroalcoholic medium using a cationic surfactant (CTMABr = cetyltrimethylammonium bromide) as structure-directing agent, and starting from molecular atrane complexes of Zr and Si as hydrolytic inorganic precursors. This preparative technique allows optimization of the dispersion of the Zr guest species in the silica walls. The bimodal mesoporous nature of the final high surface area nano-sized materials is confirmed by XRD, TEM, and N2 adsorption–desorption isotherms. The small intraparticle mesopore system (with pore sizes…

Synthesis and characterization of NdNiO3 prepared by low temperature methods

Abstract NdNiO3 has been prepared with an orthorhombic perovskite structure by a low temperature and low oxygen pressure method starting from a nickel(III) oxide precursor, β-NiO(OH). The compound LaNiO3 has also been obtained by this method. This chemical-precursor-based synthesis overcomes problems related to the use of high oxygen pressures in the synthesis.

One‐Pot Synthesis of Superparamagnetic CoO‐MCM‐41 Nanocomposites with Uniform and Highly Dispersed Magnetic Nanoclusters

Superparamagnetic CoO-MCM-41 mesoporous nanocomposites, with variable cobalt amounts, in the form of well-dispersed CoO-like clusters, were prepared in a large compositional range by a one-step reproducible procedure employing co-hydrolysis and co-condensation of the inorganic precursors in a water/triethanolamine medium. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Bases for the synthesis of nanoparticulated silicas with bimodal hierarchical porosity

Porous silicas with pore sizes at two length scales (meso and large meso/macroporous) have been prepared through a one-pot surfactant assisted procedure by using a simple template agent and starting from silicon atrane complexes as hydrolytic inorganic precursors. The special organization of these bimodal porous silicas can be related to the nanometric character of their constituent mesoporous particles. Whereas the small intra-particle mesopore system is generated by the templating effect of the surfactant, the large pore system is defined by inter-particle voids. We have studied the effect of different procedural parameters on the small pore system and also on the nucleation and growth of…

Anthrylmethylamine functionalised mesoporous silica-based materials as hybrid fluorescent chemosensors for ATP

A number of functionalised mesoporous solids containing anchored anthrylmethylamine groups have been prepared using different co-hydrolysis or grafting synthetic routes. The solids have been characterised using standard solid-state techniques. Solids with a low loading of the anthrylmethylamine probe show typical well defined and structured emission bands centred at ca. 415 nm. Addition of ATP to suspensions of these solids at pH 2.8 resulted in a quenching of the anthracene emission. These solids showed a cooperative effect that resulted in quite a remarkable improvement in ATP response with respect to the free anthrylmethylamine probe in solution. Certain prepared solids showed a remarkab…

Laser floating zone growth of textured Ag/(Bi,Pb)SrCaCuO superconductors

A new improved synthesis of the 110 K bismuth superconducting phase: freeze-drying of acetic solutions

Abstract Metastability has greatly hindered the separated synthesis of the high-temperature superconducting phases represented as (Bi1−x, Pbx)2Sr2Can−1CunO4 + 2n (n = 2, 2-2-1-2, Tc≈80 K, and n = 3, 2-2-2-3, Tc≈110 K). By careful control of the synthetic variables, it becomes possible to obtain the 110 K phase as the only superconducting one through processing of freeze-dried acetic solutions. This technique leads to homogeneously sized (5–10 μm) micaceous platelets of the superconducting material.

LOCAL STRUCTURE OF THE CuCu (EDTA) (H2O)2, 2H2O AMORPHOUS COMPLEX : A JOINT MAGNETIC, LAXS, AND MOLECULAR MECHANICS INVESTIGATION

The short range order in the amorphous CuCu (EDTA) (H2O)2, 2H2O is studied by Large Angle X-ray Scattering (LAXS) and molecular mechanics. Three conformations of the complex molecule are shown to be energetically equivalent, two of which are simultaneously present in the amorphous material.

X-ray powder diffraction data for some transition metal phosphites and hypophosphites

A set of nine transition metal oxophosphorous compounds, consisting of four hypophosphites and five phosphites has been synthesized and studied using X-ray powder diffraction techniques. The compounds are α-Mn(H2PO2)2·H2O, Co(H2PO2)2 ·0.53H2O, MCl(H2PO2)2·H2O (M = Co2+, Ni2+), M2(HPO3)2·2H2O (M = Co2+, Ni2+), and M11 (HPO3)8(OH)6 (M = Zn2+, Co2+, Ni2+). Unit cells and X-ray powder patterns are reported.

Synthesis, characterization and catalytic behavior of AlTf/UVM-7 as new green catalysts for the glycols etherification reactions

Abstract Bimodal porous Al–UVM-7 system materials with different Si-to-Al ratios were prepared using the Atrane route. These were converted in strong acid heterogeneous AlTf-based catalysts after the treatment with methanolic solutions of triflic acid. The materials so obtained were used as catalysts for the conversion of ethylene glycol (EG) and propylene glycol (PG) with octanol under solvent-free conditions. The process is selective to short ethoxylated structures resulting in the corresponding monoethers. While the conversion of EG and PG was very high (>94%) irrespective of the support characteristics, 1-octanol was transformed only in low degree (3–35%), and its conversion depends on …

Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts.

Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)-imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions p…

Control of the pore wall thickness and thermal stability in low-cost bimodal porous silicas

Abstract A new hierarchical bimodal mesoporous silica, labelled as UVM-12 (acronym of University of Valencia Materials), has been prepared by using a solution of sodium silicate as low-cost silicon source. The final self-assembling between cationic micelles of CTAB and anionic inorganic Si-based oligomers occurs in a homogeneous aqueous medium. The reaction is carried out from low-sized building blocks through a bottom-up approach. The UVM-12 solids combine two mesopore systems according to N2 adsorption–desorption isotherms, what is corroborated by TEM micrographs and XRD patterns. This material has been inorganically modified by incorporation of Al or Ti (M-UVM-12, M = Al, Ti) without alt…

Biomimetic chitosan-mediated synthesis in heterogeneous phase of bulk and mesoporous silica nanoparticles

Both bulk and mesoporous silica nanoparticles can be obtained in the form of granular aggregates using chitosan flakes as additive under very soft biomimetic reaction conditions. Puchol Estors, Victoria, Victoria.Puchol@uv.es ; El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Transition metal derivatives of low oxidation state phosphorus oxoacids: synthetic pathways and structural studies

Abstract A general synthetic approach intended to rationalize the solution preparative chemistry of transition metal phosphites and hypophosphites is presented. As previously shown for other derivatives containing also tetrahedral or pseudotetrahedral oxoanions, the hydrolytic processes affecting the cationic moieties play a determinant role on the very nature of the final solid. In fact, despite the limited number of donor atoms in the anions, the crystal chemistry of these compounds is quite intricate because of both the variety of possible cationic aggregates and the many ways to interconnect them through pseudotetrahedral anionic groups.

ChemInform Abstract: Transition Metal Derivatives of Low Oxidation State Phosphorus Oxoacids: Synthetic Pathways and Structural Studies

Abstract A general synthetic approach intended to rationalize the solution preparative chemistry of transition metal phosphites and hypophosphites is presented. As previously shown for other derivatives containing also tetrahedral or pseudotetrahedral oxoanions, the hydrolytic processes affecting the cationic moieties play a determinant role on the very nature of the final solid. In fact, despite the limited number of donor atoms in the anions, the crystal chemistry of these compounds is quite intricate because of both the variety of possible cationic aggregates and the many ways to interconnect them through pseudotetrahedral anionic groups.

Supramolecular capping-ligand effect of lamellar silica mesostructures for the one-pot synthesis of highly dispersed ZnO nanoparticles

ZnO?SiO2 lamellar nanocomposites with high zinc content (5?Si/Zn?50) have been synthesized through a one-pot surfactant-assisted procedure from aqueous solution and starting from molecular atrane complexes of Zn and Si as inorganic hydrolytic precursors. This approach allows optimization of the dispersion of the ZnO nanodomains in the silica sheets. The nature of the layered silica materials has been confirmed by x-ray diffraction. Spectroscopic (ultraviolet?visible and photoluminescence) study of these layered silica materials shows that, regardless of the Si/Zn ratio, Zn atoms are organized in well-dispersed, uniform ZnO nanodomains (about 1.2?nm) partially embedded within the silica shee…

Thalassiosira pseudonana diatom as biotemplate to produce a macroporous ordered carbon-rich material

Abstract Ordered macroporous–mesoporous carbonaceous materials were produced as a direct replica of the Thalassiosira pseudonana diatom by infiltration of the skeleton with furfuryl alcohol. The final carbon-rich material preserves the macropores of the diatom acting as bio-template and new hierarchical macro–mesopores appears as the silica is eliminated through chemical etching. The final solid can be described as an organized array of carbon macrotubes. In order to understand the progressive silica etching and the subsequent effect on the final carbon material, different etching reagents have been used. Moreover, the similar pore topology of T. pseudonana and the well known MCM-41 mesopor…

ChemInform Abstract: Synthesis and Characterization of NdNiO3 Prepared by Low Temperature Methods.

Abstract NdNiO3 has been prepared with an orthorhombic perovskite structure by a low temperature and low oxygen pressure method starting from a nickel(III) oxide precursor, β-NiO(OH). The compound LaNiO3 has also been obtained by this method. This chemical-precursor-based synthesis overcomes problems related to the use of high oxygen pressures in the synthesis.

Submicrometer CaCuO2 and Ca2CuO3 particles from bimetallic formate precursors

Abstract CaCuO2 and Ca2CuO3 are readily obtained by thermal decomposition of two new calcium and copper formates, CaCu(HCOO)4 and Ca2Cu(HCOO)6. These chemical-precursor based syntheses, while overcoming problems related to the stoichiometry of the final products, involve very short diffusion path lengths. This, in turn, results in soft treatments yielding pure phases constituted by submicrometer (≈0.4 μm) homogeneous particles.

Ordered mesoporous silicas as host for the incorporation and aggregation of octanuclear nickel(ii) single-molecule magnets: a bottom-up approach to new magnetic nanocomposite materials

Silica-based mesoporous materials have been employed as the support host for a suitably designed small octanuclear nickel(II) guest complex with a moderately anisotropic S = 4 ground spin state (D = −0.23 cm−1), which behaves as a single-molecule magnet at low temperature (TB = 3.0 K). Both unimodal MCM-41 and bimodal UVM-7 porous silica provide appropriate template conditions for the incorporation and aggregation of the Ni8 complex precursor into larger complex aggregates, showing slow relaxation of the magnetization at higher blocking temperatures than the crystalline material. By playing with the initial complex vs. silica concentration, two series of samples with varying complex loading…

Total oxidation of VOCs on Au nanoparticles anchored on Co doped mesoporous UVM-7 silica

Abstract Gold deposited on a cobalt containing siliceous mesoporous structure, UVM-7, presents a good catalytic performance in the total oxidation of propane and toluene. The presence of both gold and cobalt is necessary as bimetallic Au/Co-UVM-7 catalysts are remarkably more active than monometallic Au/UVM-7 or Co-UVM-7 catalysts. The improved activity of the bimetallic AuCo-samples if compared to gold free cobalt catalysts can be explained on the basis of the enhanced reducibility of some cobalt species in the presence of gold, which facilitates the redox cycle. This high reducibility of cobalt species in the bimetallic samples is probably due to the formation of Co 3 O 4 domains at the g…

Mesosynthesis of ZnO-SiO(2) porous nanocomposites with low-defect ZnO nanometric domains.

Silica-based ZnO-MCM-41 mesoporous nanocomposites with high Zn content (5≤Si/Zn≤50) have been synthesized by a one-pot surfactant-assisted procedure from aqueous solution using a cationic surfactant (CTMABr = cetyltrimethylammonium bromide) as structure-directing agent, and starting from molecular atrane complexes as inorganic hydrolytic precursors. This preparative technique allows optimization of the dispersion of the ZnO nanodomains in the silica walls. The mesoporous nature of the final materials is confirmed by x-ray diffraction (XRD), transmission electron microscopy (TEM) and N(2) adsorption-desorption isotherms. The ZnO-MCM-41 materials show unimodal pore size distributions without …

The ferrimagnetic compounds CoM[M’(EDTA)]2⋅4H2O(M,M’=Co,Ni): Magnetic characterization of CoCo[Ni(EDTA)2]⋅4H2O

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Low-Cost Synthesis of Bimodal Mesoporous Silica-Based Materials by Pseudomorphic Transformation.

Nanoparticulate bimodal porous silica-based materials have been prepared through a surfactant-assisted procedure by using a simple template and starting from inexpensive sodium silicate as silicon source. Different procedural variables, such as pH or the nature and concentration of the surfactant, have been explored to optimize the preparative protocol, which allows, in turn, improved understanding of the formation process. The final bulk materials (called UVM-10 or M-UVM-10) are formed by pseudomorphic transformation of fresh silica-based xerogels under mild basic conditions. The UVM-10 architecture is constructed from small mesoporous nanoparticles, the aggregation of which generates a di…

Superexchange pathways in oxovanadium(IV) phosphates

Abstract Oxovanadium(IV) phosphates show a diversity of magnetic behaviours that cannot be deduced from their respective structural features only. In part, this is due to the involvement of phosphate bridges in the spin transfer between V(IV) centres, and 31P solid state nuclear magnetic resonance becomes a key tool in determining the exchange mechanisms. The magnetic properties of a wide set of vanadium(IV) containing derivatives can be explained by realizing that a good overlap of the magnetic orbits may be achieved through paths involving phosphorus d orbitals.