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111.
The aim of present study is to select the best methodology in the frame of the Density Functional Theory (DFT), which may be employed to study the cobalamin complexes. Our discussion is limited to two approaches, one in which hybrid B3LYP and UB3LYP functionals are used, and the second in which geometry parameters are calculated within LDA-VWN functional, and energies of the investigated systems are computed within RPBE functional. Results of performed calculations show that both methodologies can be successfully applied to study cobalamin derivatives. Probably because of the small ligand binding energies in the studied complexes, the B3LYP and UB3LYP functionals may be used only to predict the pattern of changes in the binding energies. The use of the RPBE functional, originally parameterized to reproduce in a proper way the chemisorption energies of the small molecules on the metallic surfaces, allows to improve their values so as they fit into experimental data. Geometry parameters of the investigated complexes computed within both approaches are in good agreement with the experimental values. Interatomic distances are a little overestimated while calculated within both hybrid functionals, what is in contrast to VWN functional results. The latter, in general, gives shorter distances as observed experimentally. 相似文献
112.
甲烷在SrO-La2O3/CaO催化剂上的氧化偶联Ⅱ.反应动力学的研究 总被引:1,自引:0,他引:1
在20%La2O3/CaO(LC)催化剂中添加SrO(添加SrO的LC以SLC表示)明显地提高了反应活性和C2选择性。反应动力学研究表明,LC和SLC催化剂在甲烷氧化偶联反应中,在表观活化能和表观反应级数上存在很大的差异。LC催化剂在CH4转化以及C2和COx形成过程中,表观活化能大于SLC催化剂,而SLC催化剂的指前因子小于LC体系,两者存在着补偿形象。SLC催化剂的反应速率常数比kc2/kCH 相似文献
113.
以互通多孔碳(IPC)为载体,水热条件下在碳表面原位反应生成纳米结构的二氧化锰(MnO2),制备互通多孔碳/二氧化锰纳米(IPC/MnO2)复合电极材料. 采用扫描电镜(SEM),透射电镜(TEM),X射线衍射(XRD),热重分析(TGA)对其结构进行表征;采用循环伏安法、恒流充放电和交流阻抗对其电化学性能进行研究. 结果表明:生成的MnO2均匀地负载在碳的表面,形成多层次结构,并且随着温度的升高IPC表面负载的MnO2由纳米颗粒变为纳米片状结构;MnO2纳米片具有典型的K-Birnessite 型晶体结构;复合物中MnO2的含量约为34%(w). 在100 ℃制备的IPC/MnO2复合材料在三电极系统中最高比电容达到了411 F·g-1;随着反应温度的升高,比容量先增长后基本保持不变. 以IPC/MnO2为正极,活性炭(AC)为负极,1 mol·L-1 Na2SO4溶液为电解液组装成IPC/MnO2//AC 混合超级电容器,发现IPC/MnO2电极的电容器其电位窗口从1 V扩展到1.8 V,容量可达86F·g-1,且表现出良好的电容特性和大电流放电性能. 相似文献
114.
V. A. Dunyakhin O. V. Kuricheva V. V. Timofeev Yu. N. Zhitnev 《Russian Chemical Bulletin》1995,44(11):2079-2086
Multiphoton dissociation (MPD) of hexafluoropropylene oxide (HFPO) under focused CO2-laser radiation was studied. A high-energy channel of HFPO decomposition was revealed. The dependences of the MPD yield and the ratio between various channels of HFPO decomposition on the laser radiation frequency in the range from 967.7 to 1090.0 cm–1, the incident radiation energy, and the initial pressure of HFPO were obtained. A considerable contribution of thermal decomposition of HFPO occurring outside of the irradiated zone to the total yield of its decomposition was established. An explanation for the pressure dependence of the yield of HFPO decomposition was suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2174–2180, November, 1995.The authors are grateful to the Russian Foundation for Basic Research for financial support of this work (Project No. 94-03-09059). 相似文献
115.
在低钯含量活性非均布Pd/Al2O3催化剂上,实现了富氧条件下,氢部分选择性催化还原NO过程,低温、富氧条件下NO的转化率高达80%-100%。NO直接分解实验表明,600℃,NO分解转化率在无氧时为17.3%,有0.5%氧存在时接近于0。氢非选择性还原NO条件下,100℃以下,NO转化率为100%。根据实验结果及文献,推测了氢部分选择性还原NO过程中可能存在的反应,不同的反应温度下,NO脱除反应有所不同。在115℃以下,NO还原产物为NH3;115℃-155℃,NO还原产物为NH3、N2O和N2;155℃以上,NO还原产物中无NH3存在。NO还原反应与氢氧反应是平行的竞争反应。 相似文献
116.
XinZHANG DeHuaHE QiJiangZHANG BoQingXU QiMingZHU 《中国化学快报》2003,14(10):1066-1069
Comparatively high CH3OH selectivity (60.0%) and yield (6.7%) were obtained on MoOx/(LaCoO3 Co3O4) catalysts in selective oxidation of methane to methanol using molecular oxygen as oxidant. The interaction between MoOx and La-Co-oxide modified the molecular structure of molybdenum oxide and the ratio of O^-/O^2- on the catalyst surface, which controlled the catalytic performance of MoOx/(LaCoO3 Co3O4) catalysts. 相似文献
117.
WO3 and WO3:P (5 mol% H3PO4) thin films were prepared using the sol-gel route and the electrochromic properties of the films were investigated using
in situ spectroelectrochemical methods. The measurements were performed in propylene carbonate solution with 0.1 M LiClO4 as electrolyte. During the cathodic polarization at –0.8 V a blue coloration is observed with a reversible variation between
14% and 84% of the transmittance at λ=633 nm. The kinetics for the bleaching process is faster for the WO3:P film than for the undoped WO3 film.
Electronic Publication 相似文献
118.
Organic phase conversion of bulk (wurtzite) ZnO to nanophase (wurtzite and zinc blende) ZnO 总被引:1,自引:0,他引:1
Lauren P. Snedeker Aditi S. Risbud Ombretta Masala Jin Ping Zhang Ram Seshadri 《Solid State Sciences》2005,7(12):1500
We describe the all-organic phase conversion of bulk commercial ZnO in the wurtzite modification to sub-30 nm ZnO that we find to be partially in the zinc blende [, a=4.568(3) Å] modification. The conversion involves refluxing ZnO in 2,4-pentanedione (acetylacetone) at 413 K to form the zinc 2,4-pentanedionate, which is decomposed by heating at 573 K in an appropriate high-temperature solvent such as dibenzylether to form nanophase ZnO. This nanophase, partially zinc blende ZnO can also be obtained in a single step by heating commercial zinc 2,4-pentanedionate in refluxing dibenzylether. Thermodiffractometry suggests that the conversion of zinc blende ZnO to wurtzite ZnO commences near 650 K. 相似文献
119.
Aspects of the mechanism of the overall reaction between CaCO3/CaO and SO2/SO3 under oxidizing conditions are discussed. The limestone and lime sulphation processes were carried out in a thermobalance
under conditions relevant to atmospheric fluidized bed combustion. Sulphated samples, prepared in the form of cross-section
particles, were examined in a scanning electron microscope by energy-dispersive X-ray and back-scattered electron imaging.
Photomicrographs are presented. The reaction proceeded from the outer surface of the particles and along the pores. Surface
textural changes during the reaction were considered. The layer of products was identified as controlling both the rate and
extent of limestone/lime sulphation. In the products, two sulphur-bearing solids (CaSO4 and CaS) were identified. The presence of CaS, which may cause difficulties in practice, is attributed to CaSO3 disproportionation.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
120.
The surface and materials science of tin oxide 总被引:3,自引:0,他引:3
The study of tin oxide is motivated by its applications as a solid state gas sensor material, oxidation catalyst, and transparent conductor. This review describes the physical and chemical properties that make tin oxide a suitable material for these purposes. The emphasis is on surface science studies of single crystal surfaces, but selected studies on powder and polycrystalline films are also incorporated in order to provide connecting points between surface science studies with the broader field of materials science of tin oxide. The key for understanding many aspects of SnO2 surface properties is the dual valency of Sn. The dual valency facilitates a reversible transformation of the surface composition from stoichiometric surfaces with Sn4+ surface cations into a reduced surface with Sn2+ surface cations depending on the oxygen chemical potential of the system. Reduction of the surface modifies the surface electronic structure by formation of Sn 5s derived surface states that lie deep within the band gap and also cause a lowering of the work function. The gas sensing mechanism appears, however, only to be indirectly influenced by the surface composition of SnO2. Critical for triggering a gas response are not the lattice oxygen concentration but chemisorbed (or ionosorbed) oxygen and other molecules with a net electric charge. Band bending induced by charged molecules cause the increase or decrease in surface conductivity responsible for the gas response signal. In most applications tin oxide is modified by additives to either increase the charge carrier concentration by donor atoms, or to increase the gas sensitivity or the catalytic activity by metal additives. Some of the basic concepts by which additives modify the gas sensing and catalytic properties of SnO2 are discussed and the few surface science studies of doped SnO2 are reviewed. Epitaxial SnO2 films may facilitate the surface science studies of doped films in the future. To this end film growth on titania, alumina, and Pt(1 1 1) is reviewed. Thin films on alumina also make promising test systems for probing gas sensing behavior. Molecular adsorption and reaction studies on SnO2 surfaces have been hampered by the challenges of preparing well-characterized surfaces. Nevertheless some experimental and theoretical studies have been performed and are reviewed. Of particular interest in these studies was the influence of the surface composition on its chemical properties. Finally, the variety of recently synthesized tin oxide nanoscopic materials is summarized. 相似文献