The effect of support structure on CO2 hydrogenation over a rhodium catalyst supported on niobium oxide

The hydrogenation of CO₂ was investigated over a rhodium catalyst supported on niobium oxide at atmospheric pressure. Niobium oxide was prepared by the hydrolysis of niobium chloride and its crystallitic structure was controlled by calcination temperature. It was found that the activity was lower but the selectivity of C₂₊ hydrocarbons was higher for the and forms than for the and forms of the niobium oxide.     

Highly active rare earth catalysts for the solution polymerization of ε-caprolactone

Summary By using -butyrolactone (-BL) as the reaction media, highly active catalysts--light rare earth chloride-epoxidy---BL-for the solution polymerization of -caprolactone, have been obtained for the first time. With these catalyst, PCL with molecular weight as his as 40x10⁴(Mv) can be prepared at 60°C for 1.5 hr. The amount of epoxide in catalyst solution, catalyst aging temperature and time affect the catalyst activity significantly. The mechanism study shows that in -BL, the weakening of Ln-Cl bonds by the donation of coordinated -BL with Ln³⁺ and the homogenous effect promote the reaction between light rare earth chloride and epoxide. The produced rare earth alkoxide initiates CL polymerization via a coordination-insertion mechanism with Acyl-oxygen bond cleavage.     

Synergistic Catalysis of Carbon Dioxide Hydrogenation into Methanol by Yttria-Doped Ceria/γ-Alumina-Supported Copper Oxide Catalysts: Effect of Support and Dopant

Methanol synthesis from carbon dioxide hydrogenation was studied over ceria/-alumina- and yttria-doped ceria (YDC)/-alumina-supported copper oxide catalysts to seek insight into the catalysis at metal–support interfaces. It was found that, in comparison with Cu/-Al₂O₃, the Cu/CeO₂/-Al₂O₃ and Cu/YDC/-Al₂O₃ catalysts exhibited substantial enhancement in activity and selectivity toward methanol formation. The extent of enhancement was augmented by increased ceria loading on -alumina and with increased yttria doping into ceria. The enhancement is inferred to result from the synergistic effect between copper oxide and surface oxygen vacancies of ceria.     

Dynamic mechanical properties of crosslinked polyisoprene under deformation

Summary Molecular motions of elastomers under deformations were observed through dynamic mechanical measurements. Composite master curves of dynamic moduli E and E and loss tangent tan over a wide range of frequency and in a state of elongation were obtained by the time-temperature superposition procedure. It is found that both moduli increase with strain, . The slope of the dispersion curve of E become more gradual with the increase in , while that of E is almost unchanged. The increment of E is generally larger than that of E, which does not agree with the N. W. Tschoegl prediction, E ^* ()=f() E _o ^* (), where E ^* () and E _o ^* () are complex moduli at the strain of and O, respectively, and f() is the function of only . The difference in the strain dependence of E from E was found to correspond to the strain dependence of the equilibrium modulus.     

Fertilizer requirements for specified yield targets. I. Theoretical derivation of mathematical models for the computation of soil and fertilizer nutrient efficiencies

The conventional deduction procedure of computation of soil () and fertilizer () nutrient efficiencies for the amount of fertilizer required for specified yield targets does not make provision of the amount of soil nutrient derived by crops from the available pool of soil nutrients not accounted for in the amount extracted by a soil test procedure. The derivation of two mathematical models, viz., Tamil Nadu Agricultural University Model I [TNAU Model I] and Model II [TNAU Model II] is reported in this paper which aim at computing the soil () and fertilizer () nutrient efficiencies not accounted for by the conventional method.In the case of TNAU Model I, the relationship between the nutrient uptake (U) and the soil (S) and the fertilizer (F) nutrients was established by assuming a functional relationship of the type U =S +F such that 0 1 and 0 1. In TNAU Model II the same relationship was established as U =S +F + such that 0 1, 0 1 and > 0. The term in the latter model is a measure of the amount of soil nutrient the crop absorbs from a slowly available pool of nutrients not accounted for in the amounts extracted by the soil test procedure employed or applied through fertilizer.The field verification of these models is reported elsewhere.     

Lithium cycling efficiency and conductivity for γ-lactone-based electrolytes

Lithium cycling efficiency on a lithium substrate as well as conductivity were examined for-lactonebased electrolytes incorporating LiClO₄ for use in nonaqueous lithium secondary batteries.-butyrolactone (BL),-valerolactone and-octanoiclactone were used. Conductivity increased with a decrease in viscosity for lactone. Lithium cycling efficiency tended to increase with a decrease in reactivity between lithium and lactone, which would be expected from the oxidation potential for lactone. In order to decrease viscosity, tetrahydrofuran (THF) was mixed with lactone. Conductivity for lactone/THF was higher than those for systems using either lactone or THF alone. For example, 1 M LiClO₄-BL/THF (mixing volume ratio =11) showed conductivity of 13.0 × 10^–3 S cm^–1, approximately 20% higher than that for BL. Lithium cycling efficiency for BL/THF, which exceeded 90%, was also higher than that for BL. Morphology of the deposited lithium in BL/THF was smoother than that in BL and similar to that in THF, as observed with a scanning electron microscope. The reason for the enhancement of the lithium cycling efficiency for BL/THF seems to be the adsorption of THF or THF-Li⁺ around the deposited Li, which has lower reactivity to Li and higher solvation power to Li⁺ than BL.     

Molybdenum nitride for the direct decomposition of NO

The physico-chemical properties of passivated -Mo₂N have been investigated. The material showed high activities for NO direct decomposition: nearly 100% NO conversion and 95% N₂ selectivity were achieved at 450C. The amount of O₂ taken up by -Mo₂N increased with temperature rise and reached 3133.9 molg^–1 at 450C; we conclude that there formation of Mo₂O_xN_y occurred. This oxygen-saturated -Mo₂N material was catalytically active: NO conversion and N₂ selectivity were 89 and 92% at 450C. We found that by means of H₂ reduction at 450C, Mo₂O_xN_y could be reduced back to -Mo₂N and the oxidation/reduction cycle is repeatable; such a behaviour and the high oxygen capacity (3133.9 molg^–1) of -Mo₂N suggest that -Mo₂N is a promising catalytic material for automobile exhaust purification.     

Corrosion inhibition of copper in near neutral aqueous solutions by gamma-pyrodiphenone

The inhibition effect of gamma-pyrodiphenone (PD) on copper corrosion in near neutral sulphate solutions was investigated. Weight loss and polarization measurements show a high inhibition efficiency (>96%) of PD on copper corrosion at extremely low concentrations. PD suppresses active copper dissolution and oxygen reduction. The potentiodynamic cathodic reduction measurements showed an inhibition of oxide formation and stabilization of the Cu2O oxide in the presence of PD. XPS measurements suggested that the high inhibition effect of PD on copper corrosion is due to the adsorption of PD molecules, as a first stage, and the formation of a film with a polymer-like structure by coordination of PD with Cu2O on prolonged exposure.     

Lean NOx catalysis over alumina‐supported catalysts

aluminasupported catalysts show promise as lean NO_x catalysts. The role of alumina in influencing the structural and chemical properties of the active phase supported on it is discussed using some effective aluminabased lean NO_x catalysts. These include Ag/Al₂O₃, CoO_x/Al₂O₃ and SnO₂/Al₂O₃. Alumina plays an important role in stabilizing Ag in the oxidic phase and cobalt in the 2+ oxidation state. For SnO₂/Al₂O₃, alumina increases the SnO₂ surface area. On both Ag/Al₂O₃ and SnO₂/Al₂O₃, alumina also participates actively in the NO_x reduction reaction. An active organic intermediate is formed on Ag or Sn oxide which reacts with NO_x subsequently on alumina to form N₂.     

Electrochemical behaviour of viologen-cyclodextrin inclusion complexes. The case of non-alkyl group substituted viologen

The electrochemical behavior of non-alkyl substituted viologen, 4,4-dibenzyl bipyridinium (BzV), 4,4-dicyanophenyl bipyridinium (CyV) and -,-,-cyclodextrin (, , -CD) was studied using cyclic voltammetry and a spectroelectrochemical method. It was found that BzV and Fe(CN) ₆ ^4– formed a charge-transfer (CT) complex with a ratio of 21 and the colour of the solution faded with the addition of an electrolyte. This behaviour is the same as in then-heptyl viologen and ferrocyanide system [1]. BzV, -CD and -CD formed an inclusion complex only in the reduced state, whilst BzV and -CD formed an inclusion complex in both the oxidized and the reduced state. An EC scheme in which a chemical reaction follows an electrochemical reaction was considered to predominate in the BzV and -, -CD systems, while a CE scheme in which a chemical reaction preceded an electrochemical reaction predominated in the BzV and -CD system. On the other hand, CyV was found to form an inclusion complex with -, -, -CD in both the oxidized and the reduced states. therefore a CE scheme was considered to predominate in the CyV--, -, -CD systems.     

Cooperative inclusion of sodium 1-pyrenesulfonate by γ-cyclodextrin

Summary The interaction of -cyclodextrin(-CD) with sodium 1-pyrenesulfonate(PS) was studied spectrophotometrically. -CD was found to cause much larger decrease in the absorption maxima of PS than -CD. The fluorescence spectra of PS in the presence of -CD showed excimer emission, while those of PS with -CD showed only monomer emission, indicating that -CD forms 12 (-CDPS) complexes in which two PS molecules are included in the -CD cavity in a face-to-face fashion. The binding isotherm showed a sigmoidal curve. The association constants were estimated by computer simulation of the binding curve. The 12 (CDPS) complex was found to be much more stable (K=10⁶ M^–1) than the 11 complex (K=1 M^–1). At high concentration of -CD another -CD cooperates in binding two PS molecules, resulting in the formation of a 22 complex.     

Structure and thermal stability of zinc–nickel electrodeposits

ZnNi alloys were electrodeposited from a chloride bath on steel substrates. The effect of nickel bath concentration on chemical composition, structure and microstructure of the deposits is demonstrated. From 0 to 13 nickel, the phases obtained do not correspond to that reported on the thermodynamic phase diagram. It is shown that the substitution of zinc by nickel is responsible for the formation of distorted _d and _d phases corresponding to the supersaturated hexagonal phase of zinc and to the unsaturated cubic phase of Zn–Ni alloy, respectively. Differential scanning calorimetry indicates that the thermal instability of the alloys containing up to 13 wt of nickel, results from the crystallization of the phase from the _d and _d phases at around 200 °C and 250 °C, respectively.     

Catalytic oxidation of methanol to methyl formate over silver – a new purpose of a traditional catalysis system

Catalytic reaction was performed in the unregarded temperature region over silver catalysts with long catalytic lifetime for the conversion of methanol to methyl formate. O-saturated or O-saturated silver catalysts were studied individually to identify the roles of O, O in the oxidative esterification of methanol over an unsupported polycrystalline silver catalyst. A synergic process is proposed based on the coexistence of -oxygen species and -oxygen species on the surface of polycrystalline silver at about 573 K.     

Mesitylene solvated platinum atoms in the preparation of efficient supported catalysts for the dehydrogenation of methylcyclohexane to toluene

Mesitylene solvated platinum atoms have been conveniently used for the deposition of active Pt particles on -Al₂O₃ supports. The so prepared catalysts have been compared with traditionally obtained Pt/-Al₂O₃ catalysts in the dehydrogenation of methylcyclohexane to toluene, at 200 and 250 °C, showing, at low Pt loadings, a much greater specific activity.     

Pore Size Distribution and Chord Length Distribution of Porous VYCOR Glass (PVG)

A porous VYCOR-glass of porosity c 30% was analyzed by use of nitrogen adsorption (NA), mercury intrusion (MI) and small-angle scattering (SAS). The distribution density of the pore diameter was determined from the SAS experiment, based on the stereological information for a fixed order range L = 40 nm.A pore can be described by use of two random variables, which depend on each other: The pore diameter d and the chord length l. In a first step, an assumption free data evaluation method yields the second derivative of the SAS correlation function (r). Then, based on the intimate connection between (r) with random chord lengths, an interpretation of the first two mean peaks was performed. These peaks reflect the chord length distributions of pore and wall. The problem of the allocation of the peaks has been solved based on the information of the NA and MI experiments. The transformation of the distribution densities of the pore diameters V _M(d) (obtained by MI a experiment) and V _N(d) (obtained by a MI experiment) into chord length distribution densities A _M(l) and A _N(l) have allowed the clear interpretation of (r). It was possible to separate the chord distributions of the pores from those of the walls. The first (r) peak reflects the chord length distribution density (l) of the pores (first moment l¯ = 10.6 nm) and the second one that of the walls f(m) (first moment m¯ = 21 nm). It follows c 30%. The average mean chord length is d¯ _lm 15 nm. The second moment of (l) is 108 nm².Finally, from the separated function (l), the diameter distribution density of the pores V _SAS(d) has been obtained. V _SAS(d) was calculated, neither assuming a defined mathematical function type of the distribution nor a certain shape or dimension of the pore. The first and second moments of V _SAS(d) are 7 nm and 74 nm². From comparing the three distribution densities V _SAS(d), V _M(d) and V _N(d) it can be concluded that the assumption of cylindrical pores is fulfilled.While the chord length distribution density of the walls is a highly symmetrical function, which can be approximated by a Gauss term, the pores have an unsymmetrical chord distribution density with the PVG.     

The photochromism of nitrospiropyran included in γ-cyclodextrin

Summary The inclusion compounds of 1, 3, 3-trimethyl-6-nitrospiro-[2H, 1-benzo-pyran-2, 2-indoline] (NSP) with -cyclodextrin (-CD), 2,3,6,0-permethylated -CD (-MCD), and naphthyl modified -CD (-NCD) showed normal photochromism in the solid state with high light sensitivity comparable with that of NSP dispersed in polymer matrices. This is in sharp contrast with NSP in the crystalline state, which is much less photosensitive. These results suggest that the host cavity offers a sufficient free volume for phototransformation of the guest molecule. The colored form of the inclusion compounds were found to be more stable both chemically upon prolonged UV irradiation and thermally in the dark as compared with that in a PMMA film.     

The copolymerization of substituted styrenes with α-methylene-γ-butyrolactone

Summary Copolymers of halogenated styrenes and -methylene--butyrolactone were synthesized in bulk via free radical initiation. The polymerizations, in most cases, proceeded rapidly to high conversion. The high conversions obtained necessitated the use of high conversion methods to calculate reactivity ratios. In all the copolymerizations the -methylene--butyrolactone proved to be the more reactive monomer.     

Catalytic Decomposition of Hydrazine over Supported Molybdenum Nitride Catalysts in a Monopropellant Thruster

The catalytic decomposition of hydrazine over a series of MoN_x/-Al₂O₃ catalysts with different Mo loadings was investigated in a monopropellant thruster (10 N). When the Mo loading is equal to or higher than the monolayer coverage of MoO₃ on -Al₂O₃, the catalytic performance of the supported molybdenum nitride catalyst is close to that of the conventionally used Ir/-Al₂O₃ catalyst. The MoN_x/-Al₂O₃ catalyst with a loading of about 23 wt% Mo (1.5 monolayers) shows the highest activity for hydrazine decomposition. There is an activation process for the MoN_x/-Al₂O₃ catalysts at the early stage of hydrazine decomposition, which is probably due to the reduction of the oxide layer formed in the passivation procedure.     

The Preferential Oxidation of CO: Selective Combinatorial Activity and Infrared Studies

From EXAFS (extended X-ray absorption fine structure) analysis, gold was found to have mainly oxygen in its nearest coordination shell in the fresh Au/-Al₂O₃ catalyst prepared by AuCl₃ impregnation and vacuum drying at room temperature. After thermal treatment under helium, chlorine appeared within the nearest neighbors of gold and more chlorine showed up as the treatment temperature was increased from 323 to 473K. No reduced Au species was observed up to 473K under He. However, the gold became reduced during CO oxidation at 373K and above. The precursor AuCl₃ was found to deposit on -Al₂O₃ via bonding to surface hydroxyl groups. This catalyst showed nearly 100% CO conversion at 573K, but a very low activity at 373 K under the conditions used in this study. Neither the residual chlorine nor the extent of reduction can explain the low activity at lower temperatures.     

On the Promotion of Ag/γ-Al2O3 by Cs for the SCR of NO by C3H6

The promotion of Ag/-Al₂O₃ by adding alkali metals (Li, Na, K, Cs) for selective catalytic reduction of NO with C₃H₆ was studied in this work. The activity of NO reduction was enhanced by addition of Cs to Ag/-Al₂O₃ in the presence of excess oxygen and SO₂. The stability and growth of silver oxide particles were promoted and the dispersion of silver particles on -Al₂O₃ was improved by the addition of 0.5 wt% Cs and 1 wt% Cs to 2 wt% Ag/-Al₂O₃, respectively. The results were confirmed by H₂ TPR, UV-Vis DRS, TEM, and XPS.