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.

In situ FT-IR spectroscopic studies of CO adsorption on fresh Mo2C/Al2O3 catalyst

The surface sites of supported molybdenum carbide catalyst derived from different synthesis stages have been studied by in situ FT-IR spectroscopy using CO as the probe molecule. Adsorbed CO on the reduced passivated Mo2C/Al2O3 catalyst gives a main band at 2180 cm(-1), which can be assigned to linearly adsorbed CO on Mo4+ sites. The IR results show that the surface of reduced passivated sample is dominated by molybdenum oxycarbide. However, a characteristic IR band at 2054 cm-1 was observed for the adsorbed CO on MoO3/Al2O3 carburized with CH4/H-2 mixture at 1033 K (fresh Mo2C/Al2O3), which can be assigned to linearly adsorbed CO on Modelta+ (0 < delta < 2) sites Of Mo2C/Al2O3, Unlike adsorbed CO on reduced passivated Mo2C/Al2O3 catalyst, the IR spectra of adsorbed CO on fresh Mo2C/Al2O3 shows similarity to that on some of the group VIII metals (such as Pt and Pd), suggesting that fresh carbide resembles noble metals. To study the stability Of Mo2C catalyst during H-2 treatment and find proper conditions to remove the deposited carbon species, H-2 treatment of fresh Mo2C/Al2O3 catalyst at different temperatures was conducted. Partial amounts of carbon atoms in Mo2C along with some surface-deposited carbon species can be removed by the H, treatment even at 450 K. Both the surface-deposited carbon species and carbon atoms in carbide can be extensively removed at temperatures above 873 K.

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).

Spatial variability in water quality and surface sediment diatom assemblages in a complex lake basin,lake of the woods,ontario,canada

Lake of the Woods (LOW) is an international waterbody spanning the Canadian provinces of Ontario and Manitoba, and the U.S. state of Minnesota. In recent years, there has been a perception that water quality has deteriorated in northern regions of the lake, with all increase in the frequency and intensity of toxin-producing cyanobacterial blooms. However, given the lack of long-term data these trends are difficult to verify. As a first step, we examine spatial and seasonal patterns in water quality in this highly complex lake on the Canadian Shield. Further, we examine surface sediment diatom assemblages across multiple sites to determine if they track within-take differences in environmental conditions. Our results show that there are significant spatial patterns in water quality in LOW. Principal Component Analysis divides the lake into three geographic zones based primarily on algal nutrients (i.e., total phosphorus, TP), with the highest concentrations at sites proximal to Rainy River. This variation is closely tracked by sedimentary diatom assemblages, with [TP] explaining 43% of the variation in diatom assemblages across sites. The close correlation between water quality and the surface sediment diatom record indicate that paleoecological models could be used to provide data on the relative importance of natural and anthropogenic sources of nutrients to the lake.

黄土丘陵区小流域表层土壤的有机碳密度及其空间分布

通过野外调查和室内分析,采用多元线性逐步回归和地理信息系统(GIS)相结合的方法,研究了黄土丘陵区燕沟流域表层(0~20 cm)土壤的有机碳密度、空间分布及其与土地利用类型和地形因子等的关系。结果表明,流域表层土壤有机碳密度平均为1.72 kg/m2,变幅为0.97~2.93 kg/m2;土地利用类型是影响土壤有机碳密度变化的首要因子;流域土壤有机碳密度呈镶嵌的树枝状和条带状空间分布格局,其高值斑块区与乔木林地和灌木林地的分布一致,中值斑块区与草地和川坝地的分布一致,低值斑块区与梯田、果园、坡耕地、疏林地和未成林地的分布一致。流域表层土壤有机碳总储量为76.81×103t。

基于ER Mapper的水土流失地形因子提取技术初探

介绍了新一代图像处理系统ERMapper及其应用 ,分析了不同空间尺度下影响水土流失的地形因子。针对ERMapper的图像处理功能 ,对地形因子的提取技术进行了初步探讨 ,并取得了一定成果

VGIS-COLLIDE: an effective collision detection algorithm for

Collision detection is an important component in simulation applications which are based on virtual geographic information system (VGIS). In this paper, an effective collision detection algorithm for multiple objects in VGIS, VGIS-COLLIDE, is presented. The algorithm firstly integrates existing quadtree, which is the global hierarchical structure of VGIS, with axis-aligned bounding box of object to perform the broad-phase of collision detection. After that, exact collision detection between two objects which have passed the broad-phase of collision detection is performed. The algorithm makes no assumption about input primitives or object's motion and is directly applicable to all triangulated models. It can be applicable to both rigid and deformable objects without preprocessing. The performance of the algorithm has been demonstrated in several environments consisting of a high number of objects with hundreds of thousands of triangles.

Spatial-temporal characteristics of siping urban expansion based on remote sensing and GIS

Based on the RS and GIS methods, Siping city is selected as a study case with four remote sensing images in 25 years. Indices of urban morphology such as fractal dimension and compactness are employed to research the characteristics of urban expansion. Through digital processing and interpreting of the images, the process and characteristics of urban expansion are analysed using urban area change, fractal dimension and compactness. The results showed that there are three terms in this period. It expended fastest in the period of 1979~1991, and in the period of 1992~2001, the emphases on urban redevelopment made it expended slower. And this is in agreement with the Siping Statistical Yearbook. This indicates that the united of metrics of urban morphology and statistical data can be used to satisfactorily describe the process and characteristics of urban expansion. © 2008 IEEE.

Efficient red organic light-emitting diode sensitized by phosphorescent Ir compound

The efficiencies of red organic light-emitting diode (OLED) using tris-(8-hydroxy-quinoline)aluminum (Alq(3)) as host and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as dopant were greatly increased by adding a small amount (0.3 wt%) of Ir compound, iridium(III) bis(3-(2-benzothiazolyl)-7-(diethylamino)-2H-1-benzopyran-2-onato-N-',C-4) (acetyl acetonate) (Ir(C6)(2)(acac)), as a sensitizer

Pt和Ir催化剂在中性电解液中对NH_3电氧化性能

比较了Pt和Ir催化剂在中性NaClO4电解液中对NH3氧化的电催化活性和选择性。发现NH3和NH4OH在Pt和Ir催化剂上的电氧化性能相似,因而可用NH4OH代替NH3进行研究。NH4OH在Pt和Ir催化剂上氧化峰峰电流密度与NH4OH浓度呈很好的线性关系,因而Pt和Ir均能作为控制电位电解型NH3传感器的催化剂。当NH4OH浓度为0.013 mol/L时,NH3在Pt和Ir催化剂上的氧化峰分别位于0.4和0.8 V,NH4OH在Pt催化剂上的氧化峰峰电位负于在Ir催化剂上的,这是Pt催化剂的优点,但NH4OH在Ir催化剂上的氧化峰峰电流密度为Pt催化剂上的2.5倍以上,说明NH4OH在Ir催化剂上的检测灵敏度远高于在Pt催化剂上的。

超细Ir催化剂对氨氧化的电催化性能

报道了一种新型的、用NH4F作络合剂的络合还原法制备的Ir催化剂及其对氨氧化的电催化性能.结果表明,由于溶液中的Ir3+和NH4F形成络合物,因此用这种络合法制得Ir催化剂中Ir粒子的平均粒径为2.8nm,要比不加络合剂时制得的Ir催化剂中Ir粒子的平均粒径(7.5nm)小很多.所以,用络合还原法制得的Ir催化剂对氨氧化的电催化活性和稳定性都比不加络合剂时制得的Ir催化剂好很多.且该制备方法简单、实用,适用于催化剂的实际生产.

Syntheses, crystal structures, visible and near-IR luminescent properties of ternary lanthanide (Dy3+, Tm3+) complexes containing 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 1,10-phenanthroline

The ligands 4,4,4-trifluoro-1-phenyl-1.3-butanedione (Hbfa) and 1,10-phenanthroline (phen) were used to prepare ternary lanthanide (Ln) complexes [Dy(bfa)(3)phen and Tm(bfa)(3)phen]. Crystal data: Dy(bfa)(3)phen C(42)H(26)FqN(2)O(6)Dy, triclinic, P (1) over bar, a= 9.9450(6) angstrom, b = 14.0944(9) angstrom, c = 14.6043(9) angstrom, alpha = 82.104(1)degrees, beta = 87.006(1)degrees, gamma = 76.490(1)degrees, V = 1971.1(2)angstrom(3), Z = 2; Tm(bfa)(3)phen C42H26F9N2O6Tm, triclinic, P (1) over bar, a = 9.898(5)angstrom, b = 13.918(5)angstrom, c = 14.753(5)angstrom, a = 83.517(5)degrees, alpha = 86.899(5)degrees, gamma = 76.818(5)degrees, V = 1965.3(14)angstrom(3), Z = 2. The coordination number of the central Ln(3+) (Ln = Dy, Tm) ion is eight, with six oxygen atoms from three Hbfa ligands and two nitrogen atoms from the phen ligand.

Design and synthesis of near-IR luminescent mesoporous materials covalently linked with tris(8-hydroxyquinolinate) lanthanide(III) complexes

By using the bifunctional ligand, 8-hydroxyquinoline-functionalized organosilane (Q-Si), the new mesoporous material Q-MCM-41 covalently bonded with 8-hydroxyquinoline was synthesized. Through the ligand exchange reaction, the new near-infrared (NIR) luminescent mesoporous LnQ(3)-MCM-41 (Ln = Er, Nd, Yb) materials were prepared by linking the lanthanide quinolinate complexes to the ordered mesoporous Q-MCM-41 material. The LnQ(3)-MCM-41 materials were characterized by powder X-ray diffraction and N-2 adsorption/desorption, and they all show the characteristic mesoporous structure of MCM-41 with highly uniform pore size distributions.

Injection, Transport, Absorption and Phosphorescence Properties of a Series of Blue-Emitting Ir(III) Emitters in OLEDs: a DFT and Time-Dependent DFT Study

Quantum-chemistry methods were explored to investigate the electronic structures, injection and transport properties, absorption and phosphorescence mechanism of a series of blue-emitting Ir(III) complexes {[(F-2-ppy)(2)Ir(pta -X/pyN4)], where F-2-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = phenyl(1); p-tolyl (2); 2,6-difluororophenyl (3); -CF3 (4), and pyN4 = pyridine-1,2,4-tetrazolate (5)}, which are used as emitters in organic light-emitting diodes (OLEDs). The mobility of hole and electron were studied computationally based on the Marcus theory. Calculations of Ionization potentials (IPs) and electron affinities (EAs) were used to evaluate the injection abilities of holes and electrons into these complexes.