Hydrothermal synthesis, structure, and characterization of two one-dimensional chainlike hybrid complexes [(CuX)(2)(o-phen)](infinity) (X = Br, Cl; o-phen = o-phenanthroline)

Two novel organic-inorganic hybrid complexes [(CuX)(2)(o-phen)](infinity) (X = Br (1), Cl (2); o-phen = o-phenanthroline) have been synthesized hydrothermally and characterized structurally by elemental analyses, IR, ESR, XPS spectrum, TG analyses and single-crystal X-ray diffraction. Both title compounds exhibit novel one-dimensional chainlike copper halide scaffolding constructed by the unusual [Cu3X3] hexagon motifs by sharing opposite edges, where a single Cu site of each [Cu3X3] hexagon is chelated with N donors of o-phen group. To our knowledge, such basic o-phen-copper halide skeleton has not been reported hitherto. Moreover, TG analyses indicate that both title compounds possess high thermal stability.

Titanium species in titanium silicalite TS-1 prepared by hydrothermal method

The titanium species existing in titanium silicalite TS-1, which is prepared by hydrothermal method, were investigated using chemical analysis, XRD, FT-IR, Si-29 MAS NMR, UV-VIS, ESR. It has been observed that several kinds of titanium species may exist in titanium silicalite. The form that titanium atoms incorporate into the framework of titanium silicalite synthesized using tetrapropylammonium bromide (TPABr) as template differs from that using the classical method. But, the symmetry of titanium silicalite, changes from monoclinic to orthorhombic with the increase of titanium content in both methods. The Ti-O-2(-) originated from framework titanium and H2O2 has the moderate stability and may be active site in oxidation reaction. TS-1 synthesized using TPABr as template does not contain anatase, but contains a kind of partly condensed titanium species with six-fold coordination. The titanium species may correspond to 270-280 mn band in UV-VIS spectra and also can form Ti-O-2(-). But, this kind of Ti-O-2(-) is very stable and cannot be catalytic active site. So, the six-fold coordination titanium species may be inactive in both the oxidation reaction and the decomposition of H2O2. The hypothesis has been further proved by the phenomena that the titanium species is easily washed off using acid, and acid treating will not influence the catalytic performance of TS-1. (C) 2001 Elsevier Science B.V. All rights reserved.

Effect of variations in acid properties of HZSM-5 on the coking behavior and reaction stability in butene aromatization

In order to investigate the effect of acid properties on the coke behavior and stability of butene aromatization, we prepared the AHZSM-5 samples with various acid properties by the methods of hydrothernial treatment and K addition. The reaction of butene aromatization was carried out at 350 degrees C and 0.5 MPa in a continuous flow fixed bed. The characterization of the fresh/coked catalysts with NH3-TPD, N-2 adsorption-desorption measurement, and TG techniques has shown that a large amount of acid sites (high acid density) of the AHZMS-5 catalyst can cause a large quantity of coke deposit and serious channel blockage, and so result in a rapid loss of aromatization activity. On the contrary, after a great reduction in strong acid sites of AHZSM-5 catalyst resulting from some K-modification, the presence of only many weak acid sites also could not lessen the formation of coke nor improve the reaction stability of butene aromatization. Interestingly, the simultaneous reduction in the strong and weak acid sites to a desirable level by hydrothermal treating the AHZSM-5 catalyst at a proper temperature can effectively suppress the coke formation and channel blockage, and thus improve its olefin aromatization stability. (c) 2005 Elsevier B.V. All rights reserved.

Hydrothermal synthesis and characterization of ZSM-5 coatings on a molybdenum support and scale-up for application in micro reactors

A procedure has been developed to grow ZSM-5 crystals in situ on a molybdenum (Mo) support. The high heat conductivity (138 W/mK) and high mechanical stability at elevated temperatures of the Mo support allow the application of ZSM-5 coatings in micro reactors for high temperature processes involving large heat effects. The effect of the synthesis mixture composition on ZSM-5 coverage and on the uniformity of the ZSNI-5 coatings was investigated on plates of 10 X 10 mm(2). Ratios of H2O/Si = 50, SUAI = 25, and TPA/Al = 2.0 were found to be optimal for the formation of uniform coatings of 6 g/m(2) at a temperature of 150 degrees C and a synthesis time of 48 h. Scaling up of the synthesis procedure on 72 Mo plates of 40 x 9.8 x 0.1 mm 3 resulted in a uniform coverage of 14.8 +/- 0.4 g/m(2). The low deviation per individual plate (

Stable colloidal suspensions of nanostructured zirconium oxide synthesized by hydrothermal process

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermal stability and the magnetic properties of hybrid vanadium oxide-tetradecylamine nanotubes

Vanadium oxide nanotubes (NTs) were synthesized by the sol-gel method followed by a long-term hydrothermal treatment. The obtained nanotubes have a multiwall structure, and 70% of vanadium ions are in the V4+ state. This percentage was derived by evaluating three components of the magnetic susceptibility; namely, (i) the paramagnetic Curie-Weiss behavior, (ii) antiferromagnetic dimers, and (iii) magnetic trimers. The as-made NTs were annealed in situ in the cavity of the electron paramagnetic resonance (EPR) spectrometer. The line shape changes irreversibly at 390 K, and the EPR susceptibility presents an anomaly at 425 K. These changes are interpreted as a partial oxidation of the V4+ ions and consequently a decrease in the concentration of the magnetic species. The quantification of the V4+ ions of the annealed NTs reveals a diminution to 39% of V4+, a weakening of the Curie-Weiss and antiferromagnetic dimers contributions, and the suppression of magnetic trimers. Vibrational studies confirm the decrease of V4+ amount. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4749417]

Application of reactive fluid transport modeling to hydrothermal systems

A one-dimensional multi-component reactive fluid transport algorithm, 1DREACT (Steefel, 1993) was used to investigate different fluid-rock interaction systems. A major short coming of mass transport calculations which include mineral reactions is that solid solutions occurring in many minerals are not treated adequately. Since many thermodynamic models of solid solutions are highly non-linear, this can seriously impact on the stability and efficiency of the solution algorithms used. Phase petrology community saw itself faced with a similar predicament 10 years ago. To improve performance and reliability, phase equilibrium calculations have been using pseudo compounds. The same approach is used here in the first, using the complex plagioclase solid solution as an example. Thermodynamic properties of a varying number of intermediate plagioclase phases were calculated using ideal molecular, Al-avoidance, and non-ideal mixing models. These different mixing models can easily be incorporated into the simulations without modification of the transport code. Simulation results show that as few as nine intermediate compositions are sufficient to characterize the diffusional profile between albite and anorthite. Hence this approach is very efficient, and can be used with little effort. A subsequent chapter reports the results of reactive fluid transport modeling designed to constrain the hydrothermal alteration of Paleoproterozoic sediments of the Southern Lake Superior region. Field observations reveal that quartz-pyrophyllite (or kaolinite) bearing assemblages have been transformed into muscovite-pyrophyllite-diaspore bearing assemblages due to action of fluids migrating along permeable flow channels. Fluid-rock interaction modeling with an initial qtz-prl assemblage and a K-rich fluid simulates the formation of observed mineralogical transformation. The bulk composition of the system evolves from an SiO2-rich one to an Al2O3+K2O-rich one. Simulations show that the fluid flow was up-temperature (e.g. recharge) and that fluid was K-rich. Pseudo compound approach to include solid solutions in reactive transport models was tested in modeling hydrothermal alteration of Icelandic basalts. Solid solutions of chlorites, amphiboles and plagioclase were included as the secondary mineral phases. Saline and fresh water compositions of geothermal fluids were used to investigate the effect of salinity on alteration. Fluid-rock interaction simulations produce the observed mineral transformations. They show that roughly the same alteration minerals are formed due to reactions with both types of fluid which is in agreement with the field observations. A final application is directed towards the remediation of nitrate rich groundwaters. Removal of excess nitrate from groundwater by pyrite oxidation was modeled using the reactive fluid transport algorithm. Model results show that, when a pyrite-bearing, permeable zone is placed in the flow path, nitrate concentration in infiltrating water can be significantly lowered, in agreement with proposals from the literature. This is due to nitrogen reduction. Several simulations investigate the efficiency of systems with different mineral reactive surface areas, reactive barrier zone widths, and flow rates to identify the optimum setup.

Hydrothermal waves and corotating rolls in laterally heated convection in simple liquids.

The stability of a liquid layer with an undeformable interface open to the atmo- sphere, subjected to a horizontal temperature gradient, is theoretically analysed. Buoyancy and surface tension forces give rise to a basic flow for any temperature dif- ference applied on the system. Depending on the liquid depth, this basic flow is desta- bilised either by an oscillatory instability, giving rise to the so-called hydrothermal waves, or by a stationary instability leading to corotating rolls. Oscillatory perturba- tions are driven by the basic flow and therefore one must distinguish between convec- tive and absolute thresholds. The instability mechanisms as well as the di¿erent re- gimes observed in experiments are discussed. The calculations are performed for a fluid used in recent experiments, namely silicone oil of 0.65 cSt ðPr 1?4 10Þ. In partic- ular, it is shown that two branches of absolute instability exist, which may be related to the two types of hydrothermal waves observed experimentally

Hydrothermal Synthesis of Layered Double Hydroxides (LDHs) from Mixed MgO and Al2O3: LDH Formation Mechanism

The formation of MgA1 layered double hydroxide (LDH) from physically mixed MgO and Al2O3 oxides upon hydrothermal treatment has been extensively investigated, and a formation mechanism has been proposed. We observed that the formation of LDH from the oxide mixture occurs upon heating at 110 degreesC. In general, LDH is the major component while the minor phases are mainly determined by the initial pH of the oxide suspension as well as the MgO/Al2O3 ratio. The neutrality in the initial suspension results in a minor Mg(OH)(2) as the impure phase, while the alkalinity in the suspension keeps some MgO unreacted throughout the whole hydrothermal treatment. We suggest that MgO and Al2O3 be hydrated into Mg(OH)(2) and Al(OH)(3), respectively, in the initial stage for all samples. We further Suggest that in the neutral condition Mg(OH)2 be quickly dissociated to Mg2+ and OH- which then deposit on the surface of Al(OH)(3)/Al2O3 to form a M-Al pre-LDH material. Al(OH)(4)(-), ionized from Al(OH)(3) in the basic solution, deposits on the surface of Mg(OH)(2)/MgO to result in a similar MgAl pre-LDH material. Such a pre-LDH material is then well crystallized upon continuous heating via the diffusion of metal ions in the solid lattice. Such a dissociation-deposition-diffusion mechanism via two pathways has been supported by the phase composition, morphological features of crystallites, and [Mg]/[Al] ratios on the crystallite surface. and presumably applied to the general formation of LDHs with various synthetic methods. Such as coprecipitation, homogeneous preparation, and reconstruction.

Geochemical characterization and the voltammetric investigation of hydrothermal Iron speciation of samples gained during SONNE cruise SO229

Hydrothermal vent fluids are highly enriched in iron (Fe) compared to ambient seawater, and organic ligands may play a role in facilitating the transport of some hydrothermal Fe into the open ocean. This is important since Fe is a limiting micronutrient for primary production in large parts of the world's surface ocean. We have investigated the concentration and speciation of Fe in several vent fluid and plume samples from the Nifonea vent field, Coriolis Troughs, New Hebrides Island Arc, South Pacific Ocean using competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-AdCSV) with salicylaldoxime (SA) as the artificial ligand. Our results for total dissolved Fe (dFe) in the buoyant hydrothermal plume samples showed concentrations up to 3.86 µM dFe with only a small fraction between 1.1 and 11.8% being chemically labile. Iron binding ligand concentrations ([L]) were found in µM level with strong conditional stability constants up to logKFeL,Fe3+ of 22.9. Within the non-buoyant hydrothermal plume above the Nifonea vent field, up to 84.7% of the available Fe is chemically labile and [L] concentrations up to 97 nM were measured. [L] was consistently in excess of Felab, indicating that all available Fe is being complexed, which in combination with high Felab values in the non-buoyant plume, signifies that a high fraction of hydrothermal dFe is potentially being transported away from the plume into the surrounding waters, contributing to the global oceanic Fe budget.

Efficient microwave hydrothermal preparation of nanocrystalline anatase TiO2 colloids

Titanium dioxide nanocrystals are an important commercial product used primarily in white pigments and abrasives, however, more recently the anatase form of TiO2 has become a major component in electrochemical and photoelectrochemical devices. An important property of titanium dioxide nanocrystals for electrical applications is the degree of crystallinity. Numerous preparation methods exist for the production of highly crystalline TiO2 particles. The majority of these processes require long reaction times, high pressures and temperatures (450–1400 °C). Recently, hydrothermal treatment of colloidal TiO2 suspensions has been shown to produce quality crystalline products at low temperatures (<250 °C). In this paper we extend this idea utilising a direct microwave heating source. A comparison between convection and microwave hydrothermal treatment of colloidal TiO2 is presented. The resulting highly crystalline TiO2 colloids were characterised using Raman spectroscopy, XRD, TEM, and electron diffraction. The results show that the microwave treatment of colloidal TiO2 gives comparable increases in crystallinity with respect to normal hydrothermal treatments while requiring significantly less time and energy than the hydrothermal convection treatment.