Evidence for perimeter sites over SmOx-modified Rh(100) surface by CO chemisorption

SmOx modified Rh(l 0 0) surfaces have been in-situ prepared by depositing metallic Sin and subsequently oxidizing under controlled conditions, and the interaction between the lanthanide oxide and transition metal has been characterized by means of X-ray photoelectron spectroscopy (XPS) and high-resolution electron-energy-loss spectroscopy (HREELS) as well as thermal desorption spectroscopy (TDS). As evidenced, the adsorption of CO on the modified surfaces shows some different features to the original surface of Rh(l 00). The covering of SmOx blocks some sites on the surface and consequently suppresses adsorption of the typical CO species with an uptake at about 500 K, while a novel desorption peak centered at 260 K emerges in the CO TDS. Correspondingly, the XP spectrum exhibits a new C Is peak at 287.9 eV and 0 Is peak at 532.6 eV. The intensity of the low temperature peak varies with the coverage of SmOx, which shows an actual correlation to the perimeter sites of SmOx particles on the surface. (C) 2004 Elsevier B.V. All rights reserved.

In situ IR spectroscopic studies on molybdenum nitride catalysts: active sites and surface reactions

Recent IR spectroscopic studies on the surface properties of fresh Mo2N/gamma-Al2O3 catalyst are presented in this paper. The surface sites of fresh Mo2N/gamma-Al2O3, both Modelta+ (0<δ<2) and N sites, are probed by CO adsorption. Two characteristic IR bands were observed at 2045 and 2200 cm(-1), due to linearly adsorbed CO on Mo and N sites, respectively. The surface N sites are highly reactive and can react with adsorbed CO to form NCO species. Unlike adsorbed CO on reduced passivated one, the adsorbed CO on fresh Mo2N/gamma-Al2O3 behaves similarly to that of group VIII metals, suggesting that fresh nitride resembles noble metals. It is found that the surface of Mo nitrides slowly transformed into sulfide under hydrotreating conditions, which could be the main reason for the activity drop of molybdenum nitride catalysts in the presence of sulfur-containing species. Some surface reactions, such as selective hydrogenation of 1,3-butadiene, isomerization of 1-butene, and hydrodesulfurization of thiophene, were studied on both fresh and reduced passivated Mo2N/gammaAl(2)O(3) catalysts using IR spectroscopy. The mechanisms of these reactions are proposed. The adsorption and reaction behaviors of these molecules on fresh molybdenum nitride also resemble those on noble metals, manifesting the unique properties of fresh molybdenum nitride catalysts. Mo and N sites are found to play different roles in the adsorption and catalytic reactions on the fresh Mo2N/gammaAl(2)O(3) catalyst. Generally, Mo sites are the main active sites for the adsorption and reactions of adsorbates; N sites are not directly involved in catalytic reactions but they modify the electronic properties of Mo sites.

Carbon monoxide adsorption on molybdenum phosphides: Fourier transform infrared spectroscopic and density functional theory studies

Molybdenum phosphide (MoP) and supported molybdenum phosphide (MoP/gamma-Al2O3) have been prepared by the temperature-programmed reduction method. The surface sites of the MoP/gamma-Al2O3 catalyst were characterized by carbon monoxide (CO) adsorption with in situ Fourier transform infrared (FT-IR) spectroscopy. A characteristic IR band at 2037 cm(-1) was observed on the MoP/gamma-Al2O3 that was reduced at 973 K. This band is attributed to linearly adsorbed CO on Mo atoms of the MoP surface and is similar to IR bands at 2040-2060 cm(-1), which correspond to CO that has been adsorbed on some noble metals, such as platinum, palladium, and rhodium. Density functional calculations of the structure of molybdenum phosphides, as well as CO chemisorption on the MoP(001) surface, have also been studied on periodic surface models, using the generalized gradient approximation (GGA) for the exchange-correlation functional. The results show that the chemisorption of CO on MoP occurred mainly on top of molybdenum, because the bonding of CO requires a localized mininum potential energy. The adsorption energy obtained is DeltaH(ads) approximate to -2.18 eV, and the vibrational frequency of CO is 2047 cm-1, which is in good agreement with the IR result of CO chernisorption on MoP/gamma-Al2O3.

Molybdenum containing surface complex for olefin epoxidation

Silica-supported molybdenum surface complexes were prepared by the reaction between (N=) Mo(OtBu)(3) and silica via displacement of the tert-butoxy ligands for siloxyls from the silica surface. The structure of the surface molybdenum complexes was well defined by in-situ FT-IR, elemental analysis, H-1 NMR and C-13 CP/MAS NMR techniques. The surface complexes could undergo alcoholysis reaction with CD3OD and CH3OH in the same way as free (N =) Mo(OtBu)(3) and they show high catalytic activity and selectivity in olefin epoxidation. Initial rates up to 24.9 mmol epoxide (mmol Mo)(-1) min(-1) were achieved in the epoxidation of cyclohexene using TBHP as oxidant.

Microcalorimetric and IR spectroscopic studies of CO adsorption on molybdenum nitride catalysts

The adsorption of CO on both nitrided and reduced passivated Mo(2)N catalysts in either alumina supported or unsupported forms was studied by adsorption microcalorimetry and infrared (IR) spectroscopy. The CO is adsorbed on nitrided Mo(2)N catalysts on three different surface sites: 4-fold vacancies, Mo(delta+) ( 0 < delta < 2) and N sites, with differential heats of CO adsorption decreasing in the same order. The presence of the alumina-support affects the energetic distribution of the adsorption sites on the nitrided Mo(2)N, i.e. weakens the CO adsorption strength on the different sites and changes the fraction of sites adsorbing CO in a specific form, revealing that the alumina supported Mo(2)N phase shows lower electron density than pure Mo(2)N. On reduced passivated Mo(2)N catalysts the CO was found to adsorb mainly on Mo(4+) sites, although some slightly different surface Mo(delta+) d (0 < delta < 2) sites are also detected. The nature, density and distribution of surface sites of reduced passivated Mo(2)N/gAl(2)O(3) were similar to those on reduced MoO(3)/gamma-Al(2)O(3).

Abnormal phenomenon of the dependence of the retention factors for uncharged species on applied voltage in capillary electrochromatography

Polymethacrylate-based monolithic columns were prepared for capillary electrochromatography (CEC) by in situ copolymerization of butyl methacrylate (BMA), 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), and ethylene dimethacrylate (EDMA) in the presence of a porogen in fused-silica capillaries of 100 mum I.D. The abnormal phenomenon that retention factors for neutral species decreases with applied voltage in CEC was observed. Capillary electrophoresis (CE) instruments usually require a period of time to increase voltage from 0 kV to desired value, which is called as ramp time. Such ramp time and any error in the determination of dead time should be taken into account during the accurate calculation of retention factors. After the correction of the retention factors, the plots of the corrected factors for alkylbenzene versus applied voltage were made, the absolute value of the plot slopes are less than 1.8 X 10(-4), Which indicates that the corrected retention times for neutral species do not show any dependence on applied voltage. Further, the plots of the corrected retention times for acidic and basic compounds versus the reciprocal of applied voltage were drawn, where the target compounds were eluted in neutral form. The very nice linearity of the plots was obtained. The linear correlation coefficients are over 0.999. Here, the slopes of the plots represent

Catalytic decomposition of hydrazine over supported molybdenum nitride catalysts in a monopropellant thruster

The catalytic decomposition of hydrazine over a series of MoNx/gamma-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 gamma-Al2O3, the catalytic performance of the supported molybdenum nitride catalyst is close to that of the conventionally used Ir/gamma-Al2O3 catalyst. The MoNx/gamma-Al2O3 catalyst with a loading of about 23wt% Mo (1.5 monolayers) shows the highest activity for hydrazine decomposition. There is an activation process for the MoNx/gamma-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.

南沙群岛海底地貌制图研究:以1∶100万郑和群礁幅为例

中国海域辽阔,但公开发表和出版的1∶100万及更大比例尺的海底地貌图尚属空白。在综合研究已有的海底地貌分类系统的基础上,以南沙群岛郑和群礁幅为实验区,尝试建立了该海区1∶100万海洋地貌分类系统,利用历年来南沙群岛海区等深线图(1∶50万)、沉积图(1∶200万)、地质地球物理图集(1∶100万)及各种文献资料和在专家指导的基础上,绘制了该幅的海底地貌图并对该区域的地貌格局进行了分析。实验表明,通过对现有资料的综合进行1∶100万海底地貌制图是可行的。实验发现:1)等深线数据如同陆地上的等高线数据,是进行