Theoretical study on analytical potential function and spectroscopic parameters for CaF molecule

The equilibrium properties and potential energy curves of the ground electronic state of CaF have been calculated using the Brueckner Doubles calculation with a triples contribution added [BD(T)] and the gradient-corrected density functional theory with three-parameter exact exchange mixing (B3LY-P) method, with 6-311 + G*,6-311 + G(2df,2pd) and 6-311 + G(3df,3pd) basis sets. All the computational PECs are fitted to analytical potential energy functions using Murrell-Sorbie, Huxley and Tang-Toennies potentials. Based on this, the spectroscopic parameters are calculated, and then compared with some other theoretical and experimental data. (C) 2004 Elsevier B.V. All rights reserved.

Theoretical study of the femtosecond-resolved photoelectron spectrum of the NO molecule

The effect of laser fields on the NO interaction potentials is obtained by the calculation of time-resolved photoelectron spectrum (TRPES) using the time-dependent wave-packet method. The calculation not only shows that the overlap of the pump-probe pulses makes some NO molecular "invisible" states visible, but also that the coupling strength and the positions of relevant curves change on increasing the laser intensity. These changed potentials affect their dynamical behavior and influence the shape and position of each peak in TRPES. That the coupling strength of relevant potentials can be changed by the field-matter interaction is consistent with our ab initio calculations.

Characterization of the acid sites in dealuminated nanosized HZSM-5 zeolite with the probe molecule trimethylphosphine

The acid sites in dealuminated HZSM-5 zeolite with crystal sizes down to the nanoscale were firstly characterized by the probe molecule trimethylphosphine (TMP). As evidenced by the combination of P-31 CP/MAS NMR, Al-27 MAS and H-1 --> Al-27 CP/MAS NMR measurements, the Bronsted acid sites of both microsized and nanosized HZSM-5 could be decreased upon the dealumination of zeolitic framework after hydrothermal treatment. At the same time, the appearance of Lewis acid sites was observed. The dealuminated nanosized HZSM-5 is easier to form Lewis acid sites than microsized HZSM-5, and the type of Lewis acid sites in nanosized HSM-5 is more than one. In addition, the origin of Lewis acid sites is mainly associated with the aluminum at ca. 30 ppm, in the Al-27 MAS NMR spectra, and only a part of which in the dealuminated HZSM-5 zeolite acts as Lewis acid sites. (C) 2002 Elsevier Science B.V. All rights reserved.

Activated carbon supported bimetallic CoMo carbides synthesized by carbothermal hydrogen reduction

A carbothermal hydrogen reduction method was employed for the preparation of activated carbon supported bimetallic carbide. The resultant samples were characterized by BET surface area measurement, X-ray diffraction, and temperature-programmed reduction-mass spectroscopy. The results showed that nanostructured beta-Mo2C can be formed on the activated carbon by carbothermal hydrogen reduction above 700 degreesC. The particle sizes of beta-Mo2C increase with increasing reaction temperatures and Mo loading. The bimetallic CoMo carbide can be synthesized by the carbothermal hydrogen reduction even around 600 degreesC. The bimetallic CoMo carbide is from carbothermal hydrogen reduction of CoMoO4 precursor and is easily formed when the Co/Mo molar ratio is 1.0. Separation of the bimetallic CoMo carbide phase into Mo carbide and Co metal occurs when the temperature of the reduction is above 700 degreesC. The addition of a second metal such as Co and Ni, decreases the formation temperature of carbide because the second metal promotes formation of CHx species from reactive carbon atoms or groups on carbon material and hydrogen, which further carburizes oxide precursors. (C) 2003 Elsevier Science Ltd. All rights reserved.

The synthesis of nanostructured W2C on ultrahigh surface area carbon materials via carbothermal hydrogen reduction

Nanostructured tungsten carbides were synthesized, for the first time, with a size distribution of 5-12 nm on ultrahigh surface area carbon material, by carbothermal hydrogen reduction (CHR) at 850degreesC and metal Ni promoted CHR at 650 degreesC.

Catalytic partial oxidation of n-heptane for hydrogen production

Partial oxidation of n-heptane (POH) for hydrogen generation was studied over several catalysts between 700 and 850degreesC. Modified Ni-based/gamma-Al2O3 catalyst exhibited not only good catalytic activity but also good carbon deposition resistance ability. Under the modified reaction conditions, 100% n-heptane conversion and 93% hydrogen selectivity can be obtained.

The enhancement of TiO2 photocatalytic activity by hydrogen thermal treatment

In this study, conventional TiO2 powder was heated in hydrogen (H-2) gas at a high temperature as pretreatment. The photoactivity of the treated TiO2 samples was evaluated in the photodegradation of sulfosalicylic acid (SSA) in aqueous suspension. The experimental results demonstrated that the photodegradation rates of SSA were significantly enhanced by using the H-2-treated TiO2 catalysts and an optimum temperature for the H-2 treatment was found to be of 500-600 degreesC. The in situ electron paramagnetic resonance (EPR) signal intensity of oxygen vacancies (OV) and trivalent titanium (Ti3+) associated with the photocatalytic activity was studied. The results proved the presence of OV and Ti3+ in the lattice of the H2-treated TiO2 and indicated that both were contributed to the enhancement of photocatalytic activity. Moreover, the experimental results presented that the EPR signal intensity of OV and Ti3+ in the H-2-treated TiO2 samples after 10 months storage was still significant higher than that in the untreated TiO2 catalyst. The experiment also demonstrated that the significant enhancement occurred in the photodegradation of phenol using the H-2-treated TiO2. (C) 2002 Elsevier Science Ltd. All rights reserved.

Photo-induced reactions in the ion-molecule complex Mg+-OCNC2H5

Ion - molecule complexes of magnesium cation with ethyl isocyanate were produced in a laser- ablation supersonic expansion nozzle source. Photo- induced reactions in the 1: 1 complexes have been studied in the spectral range of 230 - 410 nm. Photodissociation mass spectrometry revealed the persistent product Mg+ from nonreactive quenching throughout the entire wavelength range. As for the reactive channels, the photoproducts, Mg+OCN and C2H5+, were produced only in the blue absorption band of the complex with low yields. The action spectrum of Mg+(OCNC2H5) consists of two pronounced peaks on the red and blue sides of the Mg+ 3(2)P <-- 3(2)S atomic transition. The ground state geometry of Mg+ - OCNC2H5 was fully optimized at B3LYP/6- 31 - G** level by using GAUSSIAN 98 package. The calculated absorption spectrum of the complex using the optimized structure of its ground state agrees well with the observed action spectrum. Photofragment branching fractions of the products are almost independent of the photolysis photon energy for the 3P(x,y,z) excitations. The very low branching ratio of reactive products to nonreactive fragment suggests that evaporation is the main relaxation pathway in the photo- induced reactions of Mg+ (OCNC2H5). (C) 2003 American Institute of Physics.

Molecular imprinting of nitrophenol and hydroxybenzoic acid isomers: effect of molecular structure and acidity on imprinting

Three nitrophenol isomer-imprinted polymers were prepared under the same conditions using 4-vinylpyridine as a functional monomer. Different recognition capacities for template molecules were observed for the three polymers. Another imprinting system with stronger acidity than nitrophenol isomers, 2-hydroxybenzoic acid (salicylic acid) and 4-hydroxybenzoic acid, was imprinted using 4-vinylpyridine or acrylamide as functional monomer respectively. Both 4-hydroxybenzoic acid-imprinted polymers using the two monomers showed recognition ability for the template molecule. However, when acrylamide was chosen as functional monomer, the salicylic acid-imprinted polymer showed very weak recognition for the template molecule, whereas strong recognition ability of the resultant polymer for salicylic acid was observed with 4-vinylpyridine as functional monomer. It seems that the structure and acidity of template molecules is responsible for the difference in recognition, by influencing the formation and strength of interaction between template molecule and functional monomer during the imprinting process. An understanding of the mechanism of molecular imprinting and molecular recognition of MIPs will help to predict the selectivity of MIPs on the basis of template molecule properties. Copyright (C) 2003 John Wiley Sons, Ltd.