Effects of dehydration on the apolar surface energetics of inorganic paper fillers

The surface energies of various inorganic fillers including kaolin clay, titanium dioxide, and talc were examined using inverse gas chromatography (IGC). In an earlier investigation that examined calcium carbonate fillers, dehydration by heating under a dry nitrogen purge had a substantial influence on the apolar (gammaS(LW)) and polar (gammaS(AB)) components of surface energy as measured using IGC. Using the same approach, the influence of such conditioning on several inorganic fillers used in papermaking were determined using preconditioning IGC from 100 to 300 degrees C, and sequential isothermal analysis at 100 degrees C. Results from IGC analysis of titanium dioxides (rutile and anatase) were similar to precipitated calcium carbonate (PCC) for temperatures up to 200 degrees C. PCC was significantly more energetic after preconditioning at 300 degrees C, which may indicate the onset of significant thermal decomposition that titanium dioxides will not exhibit. Kaolin clay samples had relatively high apolar surface energy similar to that of the chalk samples. Calcination gave lower gammaS(LW) values that could not be accounted for by changes in the microporous structure. More likely the differences resulted from contamination of highly energetic surface sites with adsorbates other than water. Talc samples exhibited relatively high apolar surface energies that increased with preconditioning temperature. The results provided insight into the significance of water on the final adhesion properties of fillers in the sheet structure or coating layer.     

Cyano‐Bridged Trimetallic Coordination Polymer Nanoparticles and Their Thermal Decomposition into Nanoporous Spinel Ferromagnetic Oxides

The synthesis of a novel family of cyano‐bridged trimetallic coordination polymers (CPs) with various compositions and shapes has been reported by changing the compositional ratios of Fe, Co, and Ni species in the reaction system. In order to efficiently control the nucleation rate and the crystal growth, trisodium citrate dihydrate plays an important role as a chelating agent. After the obtained cyano‐bridged trimetallic CPs undergo thermal treatment in air at three different temperatures (250, 350, and 450 °C), nanoporous spinel metal oxides are successfully obtained. Interestingly, the obtained nanoporous metal oxides are composed of small crstalline grains, and the grains are oriented in the same direction, realizing pseudo‐single crystals with nanopores. The resultant nanoporous spinel oxides feature interesting magnetic properties. Cyano‐bridged multimetallic CPs with various sizes and shapes can provide a pathway toward functional nanoporous metal oxides that are not attainable from simple cyano‐bridged CPs containing single metal ions.     

Promotion effect of adsorbed water/OH on the catalytic performance of Ag/activated carbon catalysts for CO preferential oxidation in excess H2

Activated carbon (AC) supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation (PROX) in excess H₂ was evaluated. Ag/AC catalysts, after reduction in H₂ at low temperatures (≤200 °C) following heat treatment in He at 200 °C (He200H200), exhibited the best catalytic properties. Temperature-programmed desorption (TPD), X-ray diffraction (XRD) and temperature-programmed reduction (TPR) results indicated that silver oxides were produced during heat treatment in He at 200 °C which were reduced to metal silver nanoparticles in H₂ at low temperatures (≤200 °C), simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 °C. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H₂00 treatment displayed similar PROX of CO reaction properties to Ag/SiO₂. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst.     

High purity anatase TiO(2) nanocrystals: near room-temperature synthesis, grain growth kinetics, and surface hydration chemistry

High purity, spherical anatase nanocrystals were prepared by a modified sol-gel method. Mixing of anhydrous TiCl(4) with ethanol at about 0 degrees C yielded a yellowish sol that was transformed into phase-pure anatase of 7.7 nm in size after baking at 87 degrees C for 3 days. This synthesis route eliminates the presence of fine seeds of the nanoscale brookite phase that frequently occurs in low-temperature formation reactions and also significantly retards the phase transformation to rutile at high temperatures. Heating the as-is 7.7 nm anatase for 2 h at temperatures up to 600 degrees C leads to an increase in grain size of the anatase nanoparticles to 32 nm. By varying the calcination time from 2 to 48 h at 300 degrees C, the particle size could be controlled between 12 and 15.3 nm. The grain growth kinetics of anatase nanoparticles was found to follow the equation, D(2) - D(0)(2) = k(0)t(m)e((-)(E)(a)/(RT)) with a time exponent m = 0.286(+/-9) and an activation energy of E(a) = 32 +/- 2 kJ x mol(-)(1). Thermogravimetric analysis in combination with infrared and X-ray photoemission spectroscopies has shown the anatase nanocrystals at different sizes to be composed of an interior anatase lattice with surfaces that are hydrogen-bonded to a wide set of energetically nonequivalent groups. With a decrease in particle size, the anatase lattice volume contracts, while the surface hydration increases. The removal of the surface hydration layers causes coarsening of the nanoparticles.     

In situ observation of the stability of anatase nanoparticles and their transformation to rutile in an acidic solution

Thermodynamic stability of anatase nanoparticles and their transformation behaviors to rutile phase in an acidic solution was investigated in situ at two different peptization temperatures using a freeze-drying method. When peptized at 30 degrees C, the initial product was anatase with a significantly distorted atomic structure, a significant amount of hydroxyl group and Ti3+ ions, and, thus, a thermodynamically unstable state. The instability of 30 degrees C-peptized anatase was responsible for a suitable transformation to rutile later via dissolution of the anatase to form a titanium hydroxylate, followed by reprecipitation into rutile. On the other hand, 80 degrees C-peptized anatase had a relatively more ordered atomic structure, a much reduced amount of hydroxyl group, negligible Ti3+ ions, and, thus, a thermodynamically more stable state. Plausible reasons why the 80 degrees C-peptized anatase does not transform to rutile were deduced.     

Fabrication and characterization of high-temperature microreactors with thin film heater and sensor patterns in silicon nitride tubes

In this paper the fabrication and electrical characterization of a silicon microreactor for high-temperature catalytic gas phase reactions, like Rh-catalyzed catalytic partial oxidation of methane into synthesis gas, is presented. The microreactor, realized with micromachining technologies, contains silicon nitride tubes that are suspended in a flow channel. These tubes contain metal thin films that heat the gas mixture in the channel and sense its temperature. The metal patterns are defined by using the channel geometry as a shadow mask. Furthermore, a new method to obtain Pt thin films with good adhesive properties, also at elevated temperatures, without adhesion metal is implemented in the fabrication process. Based on different experiments, it is concluded that the electrical behaviour at high temperatures of Pt thin films without adhesion layer is better than that of Pt/Ta films. Furthermore, it is found that the temperature coefficient of resistance (TCR) and the resistivity of the thin films are stable for up to tens of hours when the temperature-range during operation of the microreactor is below the so-called "burn-in" temperature. Experiments showed that the presented suspended-tube microreactors with heaters and temperature sensors of Pt thin films can be operated safely and in a stable way at temperatures up to 700 degrees C for over 20 h. This type of microreactor solves the electrical breakdown problem that was previously reported by us in flat-membrane microreactors that were operated at temperatures above 600 degrees C.     

Formation of molecular monolayers on TiO2 surfaces: a surface analogue of the Williamson ether synthesis

Strategies to modify metal oxide surfaces are important because of the increasing applications of metal oxides in catalysis, sensing, electronics, and renewable energy. Here, we report the formation of molecular monolayers on anatase nanocrystalline TiO(2) surfaces at near-ambient temperatures by a simple one-step immersion. This is achieved by an analogue of the Williamson ether synthesis, in which the hydroxyl groups of the TiO(2) surface react with iodo-alkane molecules to release HI and form a Ti-O-C surface linkage. The grafted molecules were characterized by Fourier-transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the formation of covalently bonded monolayers. Kinetic studies yielded an activation barrier of ～59 kJ/mol for the grafting reaction. Measurements of hydrolytic stability of the grafted molecules in water show that approximately half the molecules are removed within minutes to hours at temperatures of 25-100 °C with an activation energy of ～82 kJ/mol, while the remaining molecules are stable for much longer periods of time. These different stabilities are discussed in terms of the different types of Ti-O-C bonds that can form on TiO(2) surfaces.     

Effect of thermal dehydration on surface characteristics of titania gel

The surface properties of titania gel and its thermal dehydration products were investigated by nitrogen and water vapour sorption between 110 and 600°C. Structural and phase changes were studied by X-ray diffractometry and differential thermal analysis. Up to 200°C, samples were X-ray amorphous and formed anatase at 300, 450 and 600°C. The glow phenomenon is attributed to the conversion to anatase at 350°C.Thermal dehydration of the gel between 110 and 300°C and 600°C led to the widening of the pore radii of the gel. At 450°C, marked steps appeared on the nitrogen isotherm, and was accompanied by a sharp increase in nitrogen uptake. The stepwise character is attributed to the presence of a certain porosity characteristic of the gel.Heats of immersion in water depend mainly on the hydrophilic centres on the surface, whereas heats of immersion in cyclohexane are controlled by the micropore fraction of the gel.     

Surface phase behavior in Langmuir monolayers of diethylene glycol mono-n-hexadecyl ether at the air-water interface

The surface phase behavior of condensed-phase domains formed during a first-order phase transition in Langmuir monolayers of diethylene glycol mono-n-hexadecyl ether at the air-water interface has been investigated by Brewster angle microscopy and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). A variety of two-dimensional (2D) structures are observed just after the appearance of the phase transition at different temperatures. At 10 and 15 degrees C, the domains are found to be small nuclei of irregular structures. Spiral structures are observed at 20 and 22 degrees C, while striplike structures at 24 degrees C. The spiral domains attain increasingly compact shape with increasing temperature, and finally become circular at >or=26 degrees C. Increases in temperature result in dehydration in the ethylene oxide chain, which increases the hydrophobicity, and impart to the molecules a longer-chain-like character. As a result line tension increases with increasing temperature, which probably outweighs the dipole-dipole repulsions showing circular domains at higher temperatures. The PM-IRRAS measurement reveals that the nu(as)(CH(2)) mode moves to lower wave numbers indicating that the LE-LC (liquid expanded-liquid condensed) phase transition during the compression of the monolayer involves changes in the conformational order of the molecules with a preferential increase in the planner trans zigzag conformation of the hydrocarbon chains. The nu(as)(CH(2)) mode in the LC region of the isotherm shows a constant value around 2917.8 cm(-1) indicating a stable state of the monolayer with an almost all-trans conformation of the hydrocarbon chains. The downward band at 1124 cm(-1) assigned to the nu(as)(C-O-C) mode indicates that the corresponding transition dipole moment is oriented perpendicular to the water surface.     

Synthesis of aluminium borate-boron oxide and binary titanium-boron and zirconium-boron oxides from metal alkoxides and (MeO)3B3O3 in non-aqueous solvents

The reaction of metal alkoxides M(OR)4 (M = Ti, Zr; R = organyl) with (MeO)3B3O3 (1 : 0.67) in dry propan-2-one at room temperature led to gels which when dried and calcined in air for 24 h at 500-1000 degrees C afforded bi-phased mixed-oxide materials formulated as 4TiO2 x 3B2O3 and ZrO2 x B2O3 in high ceramic yields and purity; the B2O3 phases of these materials were amorphous. The materials remained amorphous upon calcination at lower temperatures. The TiO2 phase of the 4TiO2 x 3B2O3 was crystalline when calcined at higher temperatures with either anatase (600 degrees C) or rutile (>800 degrees C) being obtained. The ZrO2 phase of the ZrO2 x B2O3 was crystalline when calcined at higher temperatures and was obtained as a metastable tetragonal phase (<700 degrees C) or baddeleylite (>800 degrees C). In a similar reaction, Al(O(i)Pr)3 (2 : 1) gave a bi-phased aluminium borate-boron oxide (Al18B4O(33).7B2O3) after calcination at >700 degrees C. The dried gels and oxide materials were all characterized by elemental analysis, TGA-DSC, and powder XRD.     

Fundamental study on decontamination of tritium from gaseous phases by copper oxide

Some fundamental studies on removal of tritium from gaseous streams by a small column of copper oxide were carried out. An about 10 cm length of column packed with 100 g of copper oxide was examined on the conversion ratios of hydrogen and tritium into water. The experiment with hydrogen of 0.1% in argon showed that the logarithmic plot of remaining ratio of hydrogen by passing through the column is proportional to the reciprocal of gas flow rate and to the length of oxide column. The oxide column was also used for treating tritium-bearing waste gas from an evacuating system of alpha D-T neutron generator. It was observed that at column temperatures lower than 450 degrees C the conversion ratio of tritium in the waste gas into water is considerably smaller than that of hydrogen of 0.1% in argon.     

Evidence of CO(2) molecule acting as an electron acceptor on a nanoporous metal-organic-framework MIL-53 or Cr(3+)(OH)(O(2)C-C(6)H(4)-CO(2))

The adsorption mode of CO(2) at low coverage in the nanoporous metal benzenedicarboxylate MIL-53(Cr) or Cr(3+)(OH)(O(2)C-C(6)H(4)-CO(2)) has been identified using IR spectroscopy; the red shift of the nu(3) band and the splitting of the nu(2) mode of CO(2) in addition to the shifts of the nu(OH) and delta(OH) bands of the MIL-53(Cr) hydroxyl groups provide evidence that CO(2) interacts with the oxygen atoms of framework OH groups as an electron-acceptor via its carbon atom; this is the first example of such an interaction between CO(2) and bridged OH groups in a solid.     

Vibrational spectra of the hydrated carbonate minerals ikaite,monohydrocalcite, lansfordite and nesquehonite

The Raman (200-4000 cm(-1)) and infrared (600-4000 cm(-1)) spectra of four rare carbonate hydrate minerals are reported. These are naturally occurring and synthetic ikaite CaCO3.6H2O, and nesquehonite MgCO3.3H2O; natural monohydrocalcite CaCO3.H2O, and synthetic lansfordite MgCO3.5H2O. The spectra of synthetic ikaite partially substituted with 2H2O and also with 13C were measured, as were those of synthetic deuteriated nesquehonite. Spectra of ikaite and lansfordite, both of which decompose at room temperatures, were measured below 0 degrees C. Assignments of fundamental modes are proposed.     

Alcohol Rinsing and Crystallization Behavior of Precipitated Titanium Oxide

In our present study, the effects of alcohol washing on the crystallization behavior of precipitated titanium oxide were investigated using Fourier-transformed infrared spectroscopy (FT-IR), thermogravimetry, differential scanning calorimetry, X-ray powder diffraction, and Raman spectroscopy. Alcohol rinsing of the precipitated titania powder having an amorphous hydrated form retarded its crystallization to the anatase phase. The crystallization temperature for 390 degrees C of nonrinsed (water-washed only) powder was increased to 467 degrees C with the alcohol rinse. The retardation was attributed to the formation of oxo-alkoxides on the particle surfaces. FT-IR analysis demonstrated that the alcohol-rinsed powder had a dehydration rate much lower than that of the nonrinsed powder as temperatures were increased. Therefore, it was suggested that the presence of oxo-alkoxides in the alcohol-rinsed powder decreased the dehydration rate, which, in turn, retarded crystallization to the anatase structure. Copyright 1999 Academic Press.     

A variable-temperature diffuse reflectance infrared fourier transform spectroscopy study of the binding of water and pyridine to the surface of acid-activated metakaolin

Four metakaolins were prepared by heating a Spanish kaolin at 600, 700, 800, and 900 degrees C for 10 h. Following preliminary optimization, these metakaolins were acid activated in 6 M hydrochloric acid at 90 degrees C for 6 h; the samples calcined at 600, 700, and 800 degrees C produced the highest surface area solids and were selected for further study. Variable-temperature diffuse reflectance infrared Fourier transform spectroscopy analysis of the resulting acid-activated metakaolins (AAMKs) identified a wide range of hydrogen bond strengths in adsorbed water at room temperature. Above 300 degrees C it was possible to fit the broad hydroxyl stretching band to seven contributing components at 3730, 3700, 3655, 3615, 3583, 3424, and 3325 cm(-1). As the sample temperature was increased, the 3730 cm(-1) band increased in intensity as the water hydrogen bonded to AlOHAl was thermally desorbed. The other six bands decreased in intensity. The spectra of adsorbed pyridine indicated the presence of both Br?nsted and Lewis acid sites on the surface of the air-dried AAMKs. Preheating the AAMK at 200 degrees C prior to pyridine sorption reduced the number of Br?nsted acid sites and increased the number of thermally stable Lewis acid sites. A reduction in the amount of adsorbed pyridine after pretreating the AAMK at 400 degrees C was tentatively attributed to a reduction in surface area. This was reflected in fewer thermally stable Lewis acid sites in the AAMK pretreated at 400 degrees C compared to the number present in the sample pretreated at 200 degrees C.     

Ruthenium coatings on zirconium dioxide ceramic: Physicochemical and functional properties

Method of autoclave thermolysis of ammoniac complex compounds of ruthenium was used to obtain metallic electrically conducting ruthenium coatings with a thickness of 1–3 μm on a zirconium dioxide ceramic. Ruthenium in a coating is in the highly dispersed metallic state. A stable operation of Ru/ZrO₂/Ru as an electrochemical sensor for nitrogen and carbon oxides in a gas mixture of nitrogen with CO and NO at temperatures above 500°C was demonstrated. The results obtained indicate that the high-priced platinum can be replaced with the less expensive ruthenium in fabrication of electrochemical gas sensors.     

Removal of arsenious ion by calcined aluminum oxyhydroxide (boehmite)

Aluminum oxyhydroxide (boehmite, BE) shows adsorption ability of arsenious ion. In this study, we calcined BE in the temperature range 200-1150 degrees C, and examined the amount of arsenious ion adsorbed and adsorption mechanism. As a result, the adsorption amount of arsenious ion by BE calcined at 400 degrees C showed the highest value as compared with those by BE calcined at other temperatures. On the other hand, the amounts of arsenious ion adsorbed onto BE showed lower values at 200, 600, and >1000 degrees C than that by BE before calcination. The amount of surface hydroxyl group of calcined BE showed the highest value at the calcination temperature of 400 degrees C. As a result of X-ray analysis, BE showed boehmite structure at less than the calcination temperature of 300 degrees C, while BE was converted to the transitional state of aluminum oxide at more than 400 degrees C. From the result of the amount of arsenious ion adsorbed and FT-IR, it turned out that calcined BE dissociated water molecule when suspended in the water, hydroxyl group was generated on the surface, and the amount of arsenious ion adsorbed was increased because of the ion exchange of these hydroxyl groups with arsenious ions. It was clarified that an adsorbent with high adsorption ability of arsenious ion was obtained by calcination of BE.     

Continuous flow 2H/1H and 18O/16O analysis of water samples with dual inlet precision

A method for isotope ratio analysis of water samples is described comprising an on-line high-temperature reduction technique in a helium carrier gas. Using a gas-tight syringe, injection of 0.5 to 1 microL sample is made through a heated septum into a glassy carbon reactor at temperatures in excess of 1300 degrees C. More than 150 injections can be made per day and both isotope ratios of interest, delta2H and delta18O, can be measured with the same setup. The technique has the capability to transfer high-precision stable isotope ratio analysis of water samples from a specialized to a routine laboratory task compatible with other common techniques (automated injection for GC, LC, etc.). Experiments with an emphasis on the reactor design were made in two different laboratories using two different commercially available high-temperature elemental analyser (EA) systems.In the Jena TC/EA unit, sample-to-sample memory (single injection) has been reduced to approximately 1% and high precision of about 0.1 per thousand for delta18O and < 1 per thousand for delta2H has been achieved by a redesign of the glassy carbon reactor and by redirecting the gas flow of the commercial TC/EA unit. With the modified reactor, the contact of water vapour with surfaces other than glassy carbon is avoided completely. The carrier gas is introduced at the bottom of the reactor thereby flushing the outer tube compartment of the tube-in-tube assembly before entering the active heart of the reactor.With the Leipzig high-temperature reactor (HTP) similar precision was obtained with a minor modification (electropolishing) of the injector metal sleeve. With this system, the temperature dependence of the reaction has been studied between 1100 and 1450 degrees C. Complete yield and constant isotope ratio information has been observed only for temperatures above 1325 degrees C. For temperatures above 1300 degrees C the reactor produces an increasing amount of CO background from reaction of glass carbon with the ceramic tube. This limits the usable temperature to a maximum of 1450 degrees C. Relevant gas permeation through the Al2O3 walls has not been detected up to 1600 degrees C.     

Density functional theory study of CO adsorption on molybdenum sulfide

CO adsorption on four MoSx (stoichiometric and nonstoichiometric) clusters has been investigated by using density functional method. It is found that CO prefers adsorption on the coordinatively unsaturated (1010) surface. The adsorption energy of high coverage shows the additivity as compared with that of one CO adsorption, and there is no significant repulsive interaction between the end-on adsorbed CO probes. The computed CO stretching frequencies (2000-2080 cm(-1)) agree perfectly with the experimental data (a broad band centered at 2070 cm(-1) with a tail extent to 2000 cm(-1)). No bridged CO adsorption is favored energetically under high CO concentration, and this might explain the catalytic ability of MoSx for C1 products instead of higher hydrocarbons and alcohols.     

The cation-deficient Ruddlesden-Popper oxysulfide Y2Ti2O5S2 as a layered sulfide: topotactic potassium intercalation to form KY2Ti2O5S2

Potassium intercalation into the cation-deficient n = 2 Ruddlesden-Popper oxysulfide Y(2)Ti(2)O(5)S(2) to form KY(2)Ti(2)O(5)S(2) has been carried out by reaction of the oxysulfide with potassium vapor in sealed metal tubes at 400 degrees C, potassium naphthalide in THF at 50 degrees C, or potassium in liquid ammonia at temperatures as low as -78 degrees C. Insertion of potassium is topotactic, and although a site 12-coordinate by oxide ions is vacant in the perovskite-type oxide slabs of the structure, potassium is too large to enter this site via the 4-coordinate window, and instead enters the rock-salt-type sulfide layers of the structure which necessitates a 30% increase in the lattice parameter c normal to the layers. In contrast with one of the sodium intercalates of Y(2)Ti(2)O(5)S(2) (beta-NaY(2)Ti(2)O(5)S(2)) in which sodium occupies a tetrahedral site in the sulfide layers, potassium favors an 8-coordinate site which necessitates a relative translation of adjacent oxide slabs. KY(2)Ti(2)O(5)S(2) is tetragonal: P4/mmm, a = 3.71563(4) A, c = 14.8682(2) A (at 298 K), Z = 1. Although the resistivity (3.4(1) x 10(3) Omega cm) is larger than would be expected for a metal, temperature independent paramagnetism dominates the magnetic susceptibility, and the material is electronically very similar to the analogous sodium intercalate beta-NaY(2)Ti(2)O(5)S(2) which features reduced-titanium-containing oxide layers of very similar geometry and electron count.