The reaction route and active site of catalytic decomposition of hydrazine over molybdenum nitride catalyst

The catalytic properties of the passivated, reduced passivated, and fresh bulk molybdenum nitride for hydrazine decomposition were evaluated in a microreactor. The reaction route of hydrazine decomposition over molybdenum nitride catalysts seems to be the same as that of Ir/gamma-Al2O3 catalysts. Below 673 K, the hydrazine decomposes into N-2 and NH3. Above 673 K, the hydrazine decomposes into N-2 and NH3 first, and then the produced NH3 further dissociates into N-2 and H-2. From the in situ FT-IR spectroscopy, hydrazine is adsorbed and decomposes mainly on the Mo site of the Mo2N/gamma-Al2O3 catalyst. (C) 2004 Elsevier Inc. All rights reserved.

ELECTROCATALYTIC OXIDATION AND FLOW DETECTION OF HYDRAZINE COMPOUNDS IN LIQUID-CHROMATOGRAPHY AT A VITAMIN-B-12 ADSORBED GLASSY-CARBON ELECTRODE

A vitamin B-12 chemically modified electrode (CME) was constructed by adsorption of vitamin B-12 onto a glassy carbon surface. The electrode catalyzes the electrooxidation of hydrazine compounds over a wide pH range. The electrocatalytic behavior of hydrazines is elucidated with respect to the CME preparation conditions, solution pH, operating potential, mobile phase flow rate, and other variables. When applied to liquid chromatographic detection of the analytes, the vitamin B-12 CME yielded a linear response range over 2 orders of magnitude, and detection limits at the picomole level. The vitamin B-12 CME offers acceptable catalytic stability in both batch and flow systems.

FLOW-INJECTION AMPEROMETRIC DETECTION OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION AT A PRUSSIAN BLUE FILM-MODIFIED ELECTRODE

A Prussian Blue-modified glassy carbon electrode prepared by simple adsorption exhibited excellent electrocatalytic activity in the oxidation of hydrazine in acidic media. A film of the perfluorosulphonic acid polymer Nafion coated on top of the Prussian Blue-modified glassy carbon electrode can improve the mechanical stability of the Prussian Blue layer in the flow stream. Hydrazine was detected by flow-injection analysis at the modified electrode with high sensitivity. The limit of detection was 0.6 ng.

Microcalorimetric studies of the iridium catalyst for hydrazine decomposition reaction

Microcalorimetric studies of H-2, NH3 and O-2 adsorption, as well as the NH3 decomposition activities evaluation were used to characterize the iridium catalysts for hydrazine decomposition with different supports (Al2O3, SiO,) and iridium contents (1.8, 10.8 and 22.1%). The higher H-2 chemisorption amounts on Ir/Al2O3 catalysts than those on the corresponding Ir/SiO2 counterparts revealed that the strong interaction of iridium and Al2O3 led to higher dispersion of iridium on Ir/Al2O3 catalysts than on Ir/SiO2 catalysts. The larger increase in strong H-2 adsorption sites on highly loaded Ir/Al2O3 than the corresponding Ir/SiO2 ones could be attributed to the interaction not only between iridium atoms but also between iridium and Al2O3. The microcalorimetric results for NH3 adsorption showed that no apparent chemisorption of NH3 existed on Ir/SiO2 catalysts while NH3 chemisorption amounts increased on Ir/Al2O3 catalysts with iridium loadings, which arose from the interaction of the catalysts support of Al2O3 With chloride anion. Both highly dispersed iridium active sites and chloride anion on Ir/Al2O3 catalysts could be beneficial to the intermediate NH3 decomposition in N2H4 decomposition. The similar O-2 plots of differential heat versus normalized coverage on Ir/Al2O3 and Ir/SiO2 catalysts could not be due to the metal-support interaction, but to the formation of strong Ir-O bond. (C) 2005 Elsevier B.V. All rights reserved.

Hydrazine-hydrate intercalated halloysite under controlled-rate thermal analysis conditions

The thermal behaviour of halloysite fully expanded with hydrazine-hydrate has been investigated in nitrogen atmosphere under dynamic heating and at a constant, pre-set decomposition rate of 0.15 mg min-1. Under controlled-rate thermal analysis (CRTA) conditions it was possible to resolve the closely overlapping decomposition stages and to distinguish between adsorbed and bonded reagent. Three types of bonded reagent could be identified. The loosely bonded reagent amounting to 0.20 mol hydrazine-hydrate per mol inner surface hydroxyl is connected to the internal and external surfaces of the expanded mineral and is present as a space filler between the sheets of the delaminated mineral. The strongly bonded (intercalated) hydrazine-hydrate is connected to the kaolinite inner surface OH groups by the formation of hydrogen bonds. Based on the thermoanalytical results two different types of bonded reagent could be distinguished in the complex. Type 1 reagent (approx. 0.06 mol hydrazine-hydrate/mol inner surface OH) is liberated between 77 and 103°C. Type 2 reagent is lost between 103 and 227°C, corresponding to a quantity of 0.36 mol hydrazine/mol inner surface OH. When heating the complex to 77°C under CRTA conditions a new reflection appears in the XRD pattern with a d-value of 9.6 Å, in addition to the 10.2 Ĺ reflection. This new reflection disappears in contact with moist air and the complex re-expands to the original d-value of 10.2 Å in a few h. The appearance of the 9.6 Å reflection is interpreted as the expansion of kaolinite with hydrazine alone, while the 10.2 Å one is due to expansion with hydrazine-hydrate. FTIR (DRIFT) spectroscopic results showed that the treated mineral after intercalation/deintercalation and heat treatment to 300°C is slightly more ordered than the original (untreated) clay.

Synthesis, characterization of palygorskite supported zero-valent iron and its application for methylene blue adsorption

In this work, natural palygorskite impregnated with zero-valent iron (ZVI) was prepared and characterised. The combination of ZVI particles on surface of fibrous palygorskite can help to overcome the disadvantage of ultra-fine powders which may have strong tendency to agglomerate into larger particles, resulting in an adverse effect on both effective surface area and catalyst performance. There is a significant increase of methylene blue (MB) decolourized efficiency on acid treated palygorskite with ZVI grafted, within 5 mins, the concentration of MB in the solution was decreased from 94 mg/L to around 20 mg/L and the equilibration was reached at about 30 to 60 mins with only around 10 mg/L MB remained in solution. Changes in the surface and structure of prepared materials were characterized using X-ray diffraction (XRD), infrared (IR) spectroscopy, surface analysing and scanning electron microscopy (SEM) with element analysis and mapping. Comparing with zero-valent iron and palygorskite, the presence of zero-valent iron reactive species on the palygorskite surface strongly increases the decolourization capacity for methylene blue, and it is significant for providing novel modified clay catalyst materials for the removal of organic contaminants from waste water.

Effect of thermal treatment on adsorption-desorption of ammonia and sulfur dioxide on palygorskite : change of surface acid-alkali properties

Thermally activated Palygorskite (Pg) has been found to be a good adsorbent material for ammonia (NH3) and sulfur dioxide (SO2). This research investigated the effect of thermal treatment on pore structure and surface acid-alkali properties of Pg through the adsorption-desorption of NH3 and SO2. The results showed that, up to 200 °C, the adsorption of NH3 on Pg was significantly higher than SO2. This was due to NH3 being adsorbed in the internal surface of Pg and forming hydrogen bonds (H-bonds) with coordinated water. The increase in thermal treatment temp. from 150 to 550 °C, showed a gradual decrease in the no. of surface acid sites, while the no. of surface alk. sites increased from 200 to 400 °C. The change of surface acidity-alk. sites is due to the collapse of internal channels of Pg and desorption of different types of hydroxyls assocd. with the Pg structure.

Surface modification of alumina nanofibres for the selective adsorption of alachlor and imazaquin herbicides

The effective removal of pollutants using a thermally and chemically stable substrate that has controllable absorption properties is a goal of water treatment. In this study, the surfaces of thin alumina (γ-Al2O3) nanofibres were modified by the grafting either of two organosilane agents, 3-chloro-propyl-triethoxysilane (CPTES) and octyl-triethoxysilane (OTES). These modified materials were then trialed as absorbents for the removal of two herbicides, alachlor and imazaquin from water. The formation of organic groups during the functionalisation process established super hydrophobic sites on the surfaces of the nanofibres. This super hydrophobic group is a kind of protruding adsorption site which facilitates the intimate contact with the pollutants. OTES grafted substrate were shown to be more selective for alachlor while imazaquin selectivity is shown by the CPTES grafted substrate. Kinetics studies revealed that imazaquin was rapidly adsorbed on CPTES-modified surfaces. However, the adsorption of alachlor by OTES grafted surface was achieved more slowly.

Mechanism of p-nitrophenol adsorption from aqueous solution by HDTMA+-pillared montmorillonite : implications for water purification

HDTMA+ pillared montmorillonites were obtained by pillaring different amounts of the surfactant hexadecyltrimethylammonium bromide (HDTMAB) into sodium montmorillonite (Na-Mt) in an aqueous solution. The optimum conditions and batch kinetics of sorption of p-nitrophenol from aqueous solutions were reported. The solu-tion pH had a very important effect on the sorption of p-nitrophenol. The maximum p-nitrophenol absorption/adsorption occurs when solution pH (7.15~7.35) is approx-imately equal to the pKa (7.16) of the p-nitrophenol ion deprotonation reaction. X-ray diffraction analysis showed that surfactant cations had been pillared into the interlayer and the p-nitrophenol affected the arrangement of surfactant. With the increased con-centration of surfactant cations, the arrangement of HDTMA+ within the clay inter-layer changes and the sorption of p-nitrophenol increases. HDTMA+ pillared mont-morillonites are more effective than Na-Mt for the adsorption of p-nitrophenol from aqueous solutions. The Langmuir, Freundlich and dual-mode sorption were tested to fit the sorption isotherms.

An infrared study of adsorption of paranitrophenol on mono, di and trialkyl surfactant intercalated organoclays

Infrared spectroscopy has been used to study the adsorption of paranitrophenol on mono, di and tri alkyl surfactant intercalated montmorillonite. Organoclays were obtained by the cationic exchange of mono, di and tri alkyl chain surfactants for sodium ions [hexadecyltrimethylammonium bromide (HDTMAB), dimethyldioctadecylammonium bromide (DDOAB), methyltrioctadecylammonium bromide (MTOAB)] in an aqueous solution with Na-montmorillonite. Upon formation of the organoclay, the properties change from strongly hydrophilic to strongly hydrophobic. This change in surface properties is observed by a decrease in intensity of the OH stretching vibrations assigned to water in the cation hydration sphere of the montmorillonite. As the cation is replaced by the surfactant molecules the paranitrophenol replaces the surfactant molecules in the clay interlayer. Bands attributed to CH stretching and bending vibrations change for the surfactant intercalated montmorillonite. Strong changes occur in the HCH deformation modes of the methyl groups of the surfactant. These changes are attributed to the methyl groups locking into the siloxane surface of the montmorillonite. Such a concept is supported by changes in the SiO stretching bands of the montmorillonite siloxane surface. This study demonstrates that paranitrophenol will penetrate into the untreated clay interlayer and replace the intercalated surfactant in surfactant modified clay, resulting in the change of the arrangement of the intercalated surfactant.

Characterisation of organoclays and adsorption of p-nitrophenol : environmental application

Organoclays were synthesised through ion exchange of a single surfactant for sodium ions, and characterised by a range of method including X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and transmission electron microscopy (TEM). The change in surface properties of montmorillonite and organoclays intercalated with the surfactant, tetradecyltrimethylammonium bromide (TDTMA) were determined using XRD through the change in basal spacing and the expansion occurred by the adsorbed p-nitrophenol. The changes of interlayer spacing were observed in TEM. In addition, the surface measurement such as specific surface area and pore volume was measured and calculated using BET method, this suggested the loaded surfactant is highly important to determine the sorption mechanism onto organoclays. The collected results of XPS provided the chemical composition of montmorillonite and organoclays, and the high-resolution XPS spectra offered the chemical states of prepared organoclays with binding energy. Using TGA and FT-IR, the confirmation of intercalated surfactant was investigated. The collected data from various techniques enable an understanding of the changes in structure and surface properties. This study is of importance to provide mechanisms for the adsorption of organic molecules, especially in contaminated environmental sites and polluted waters.