B3LYP/6-311CCG (3df,3pd) and CCSD (T)/6-311CCG (2d,2p) calculations show that the reaction of Li2O with CH4 can proceed by two distinct reaction channels, that is, channel A: Li2OCCH4/CH3LiCLiOH, and channel B: Li2OCCH4/CH3OHCLi2 (1SC). The former is predicted to be endothermic by about 111.1 kJ/mol with an energy barrier of 157.4 kJ/mol, and the latter endothermic by about 219.1kJ/mol with an energy barrier of 322.3kJ/mol. With the relatively lower energy required, the formation of CH3Li would be more feasible comparing to the formation of methanol with a rather higher energy barrier.

The reaction singlet potential energy curves of reactions Ni (d9s13D)+CH2 (3B1)→H2+ NiC and Ni (d9s13D) + CH2 (3B1)→trans-HNiCH, and the electronic and geometric structures and vibrational frequencies of all intermediates and transition states in the reactions above have been studied at B3LYP/6-311+ G (2d,2p) and B3LYP/6-311þþG (3df,2p) levels. The former reaction is predicted to be endothermic by about 32.9kJmol21, and the latter exothermic by about 65.9kJ mol21. At low energy levels, the formation of trans-HNiCH would be the dominant process, while at high energy levels, the formation of H2+ NiC would be the dominant process.

The singlet state potential energy curve of the reaction NI (d101S) +CH4→NICH2+H2, the electronic and geometric structures and vibrational frequencies of all intermediates and transition states in the reaction path were studied by B3LYP method. In the reaction, an atom-molecule complex NiCCH4acting as precursorin the breaking of C-H bond was predicted. For NiCH4, a frequency of 2988cm-1 is typical of methane molecularly adsorbed on Ni.Frequencies of 2531 and 2438cm-1are indicative of the formation ofa C-H...metal bond and a frequency of 355-1is typicalof Ni-CH4 stretching mode.A nickel hydrdo-methyl complex HniCH3is frmed upon the very low bamier in sertion of Ni0into a C-H bond of CH4. For HNiCH3,frequencies of 2980 and 2853cm-1 are representative of CH3 coadsorbed with H on Ni, and a frequency of 565cm-1 is indicative of the HNi-CH3 stretching mode. Adihydrogen complex of atom ni ckel carbene (H2) NiCH2 proceeds from the migration of a-hydrogen from carbon to metal with considerably large barrier,indicating that this is the rate-determining step in the whole spectively.Sybsequently, the whole reaction .For (H2) NiCH2, frequencies of 3344 and 694cm-1 are characteristic of H-H and (H2) NI-CH2 stretching modes respectively.Subsequently,the final products NiCH2 and H2 evolve after the elimination of H2 fron the transition-metal center.For NiCH2, a frequency of 754cm-1 is assigned to the Ni-Ch2 stretching mode. For all intermediates and transition states in the reaction path,the electron transfer is exclusively from nickel to carbon. Ingeneral, the overall reaction is mildly exothermic by1.6KJmol-1relative to Ni(d101S)+CH4reactants.

The interaction of CO and CO2 with nickel has been studied comparatively using the ab initio method. The results show that the carbon-oxygen bond is weakened when CO interacts with nickel, and the weakening is more obvious in the bridged adsorbed model than that in the linear one. The calculated vibrational frequencies are close to those found experimentally. Three interaction modes of CO2 with a Ni2 small cluster are found to be possible in which the most stable one has a bidentate structure, i.e. two oxygen atoms bonded to two adjacent nickel atoms, respectively. The weakening of the carbon-oxygen bond is more remarkable in the CO2 adsorbed model than in the CO adsorbed one. The Ni2 cluster structure suitable for CO2 is different from that for CO except that the Ni-Ni interatom distance in the CO bridged adsorbed species is significantly close to that in CO2 bidentate species.

The hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by Zn (II), Cu (II) and Co(II) complexes of imidazole groups have been investigated kinetically in the pH range 6.0-8.0 at the presence of three kinds of surfactants and 25.0±0.01℃, respectively. The results indicated that Zn (II) complex exhibit a great catalytic function in micellar solution with higher pH value, but when reactions were performed in weak acid solutions, Cu (II) complex catalyzed the hydrolysis of PNPP more efficiently than Zn (II) and Co (II) complexes did, which may be attributable to the different ionization states of the corresponding complexes in micellar media with different pH values and the different nucleophilic ability of active species in different complexes. In addition, these complexes showed more reactivity in zwitterionic (LSS) and nonionic (Brij35) micelles than that in cationic (CTAB) micelle, which may be explained by the electrostatic interaction between metal ions of these complexes and the head groups of surfactants or the substrate. The relative kinetic and thermodynamic parameters were obtained by kinetic analysis employing ternary complex model for metallomicellar catalysis.

The reactions of (1) CH4 + MgO → MgOH• + CH3• and (2) CH4 + MgO → Mg + CH3OH have been studied on the singlet spin state potential energy surface at the MP2/6-311+G(2d,2p) level. These two reaction channels, both involving intermediates and transition states, have been rationalized by the structures of the species involved, natural bond orbital (NBO), and vibrational frequency analysis. We have considered two initial interacting models between CH4 and MgO: a collinear C-H approach to the O end of the MgO forming the MgOCH4 complex with C3V symmetry and three hydrogen atoms of the methane point to the Mg end of the MgO forming the OMgCH4 complex with C1 symmetry. The calculations predict that reactions 1 and 2 are exothermic by 39.8 and 86.5kJmol-1, respectively. Also, the former reaction proceeds more easily than the latter, and the complex HOMgCH3 is energetically preferred in the reaction of MgO + CH4.

The liquid-phase direct catalytic oxidation of benzene to phenol was studied at room temperature using vanadium-substituted heteropolyacids as catalysts. Glacial acetic acid was employed as the solvent for the first time, while hydrogen peroxide was used as the oxidant. A yield of 26% and a selectivity of 91%, respectively, were obtained. The as-prepared phenol was separated by column chromatography and was characterized by infrared and mass spectrometry. The catalysts have been characterized by lemental analysis, thermal gravimetric analysis, infrared spectroscopy, UV–vis spectroscopy, X-ray iffraction, and 31P NMR and 51V NMR techniques. The effects of various reaction parameters, such as solvent, reaction temperature, reaction time and the amount of hydrogen peroxide used, were studied. The effects of different vanadium species on the catalytic performance were also studied. Glacial acetic acid was found to be the most suitable solvent among the solvents used in present work. An appropriate molar ratio of H2O2 to benzene of 1.7, and a favorable reaction time of 100min were optimized. H4PMo11VO40 13H2O was found to be the most active in terms of turnover based on vanadium atom and the most stable catalyst.

Temperature-programmed reduction (TPR) and continuous stepwise reduction-methanation (CSRM) have been used to identify and separate the active phases of Ni/Al2O3 catalyst. It is found that there are four hydrogen consumption peaks representing four nickel species on Al2O3; the peak temperatures for three of them are below 673K when the reduction temperature does not exceed to 973K. For the methanation of both CO and CO2, three distinct active phases are discovered, the activation temperatures of which coincide with the peak temperatures of the first three TPR peaks, respectively. This indicates that different oxidized nickel species exist on Al2O3 prior to reduction and form different active phases for the methanation of both CO and CO2 after reduction. The methanation activities on each phase for both CO and CO2 in terms of CH4 yield or initial methanation temperature and turnover number differ significantly. Each phase also exhibits different activity for CO and CO2 methanation. It is suggested that the mechanism of methanation for CO or CO2 on different phases may vary, and that the mechanism for CO and CO2 on the same phase may also vary. CSRM is convenient for separating different active phases for the methanation of both CO and CO2 on Ni/Al2O3 catalyst.

The reactions of hydroquinone with hydrogen peroxide catalyzed by transition metal ions Cu2+, Fe2+, Fe3+, Co2+ and Mn2+ were investigated in aqueous solution at 25℃. Two copper (II) complexes (bis(dimethylglyoxime) copper (II) and 5, 7, 7, 12, 14, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradeca-4,11-dienatocopper (II) iodide) were prepared. Their catalytic activities on this oxidation were kinetically investigated in aqueous solution and in cetyltrimethylammonium bromide (CTAB) micellar solution at 25℃. The kinetic equations for micellar catalysis and metallomicellar catalysis were established, respectively. CTAB micelle enhances the reaction rate due to its concentrated and electrostatic effects on substrates and/or intermediate. Metallomicelle exhibits remarkable catalytic activity on this oxidation reaction, which is attributed to the active center and the microenvironment effects. Metallomicelle enhances the rate of reaction by activating hydroquinone anion. The presence of co-ligand of imidazole (or pyridine) remarkably increases the catalytic activity of metal complex in micelle system in contrast to it lowers the activity of the complex in aqueous solution. Metallomicelles could be treated as the mimic models of peroxidase.

The reactions between Ni (d101S) and CH4 have been carried out at the B3LYP/6-311+G (2d, 2p) and B3LYP/6-311++G (3df,2p) theoretical levels. The reaction path in which the intermediates transfer from one to another via transition state is rationalized by their structures and natural bond orbital analysis. The reactions of Ni+CH4→NiCH2+H2, Ni+CH4→NiCH3+H and Ni+CH4→NiH+ CH3 are predicted to be endothermic, and the reaction Ni+CH4→NiH+CH3 is the easiest to occur.