Surface Properties of Cu Doped La-Ni Intermetallic Compounds

A series of Cu-doped La-Ni intermetallic compounds(LaN5-xCux, x = 0-4) was studied. The bulk structure and surface composition of the samples were detected before and after they were used as catalyst for nitrobenzene hydrogennation. The catalytic properties of the intermetallic compounds depend on the surface region composition, especially on the valence of the metal ions.     

Features of the formation of silver nanoparticles on the silicon nitride surface

Special features of the formation of particles of a silver-containing catalyst phase on a silicon nitride surface in relation to the mode of the active component deposition were studied. The influence of a redox medium of the catalytic reaction of the ethylene glycol selective oxidation to glyoxal on the final composition and structure of silver catalysts was studied.     

Catalytic enantioselective construction of tetrasubstituted carbons by self-assembled poly rare earth metal complexes

Rare earth metal-based enantioselective catalysts that can promote practical cyanation reactions of ketones and ketoimines were developed. These catalytic enantioselective tetrasubstituted carbon-forming reactions are useful platforms for the synthesis of biologically active compounds. ESI-MS and crystallographic studies of the asymmetric catalysts revealed that the active catalysts are polymetallic complexes produced through the assembly of modules. The higher-order structure of the polymetallic complexes has strong effects on catalyst activity and enantioselectivity. Controlling the higher-order structure of artificial polymetallic asymmetric catalysts is a new strategy for optimizing asymmetric catalysts. Recent progress in this approach is also described.     

改性SiO2对铁基催化剂H2、CO吸附及加氢性能的影响

采用溶胶凝胶方法通过掺杂修饰剂M（M=Mn、Zn、Zr、Sr）制备出改性SiO₂载体,再用浸渍法将Fe元素负载于该载体上制成系列催化剂。采用X射线衍射（XRD）、氮气物理吸附-脱附、X射线光电子能谱（XPS）等手段表征了催化剂的织构性质、晶相组成和电子性质。利用程序升温手段研究了催化剂的H₂还原吸附性质和CO加氢性能。借助动力学分析方法研究了催化剂与H之间的相互作用。结果表明,少量掺杂的修饰剂对催化剂的Fe物相组成以及表面Fe物种电子状态基本没有影响,但降低了催化剂的比表面积以及活性相分散度,削弱了对H₂的吸附能力,降低催化剂的H₂脱附活化能。Zn、Zr的掺杂抑制了催化剂的还原,而Mn、Sr的掺杂却促进催化剂的还原。Mn、Zn、Zr的掺杂抑制催化剂表面CO的解离吸附,Sr则促进CO的解离吸附,Mn、Zn、Zr、Sr均促进低温区间C-C耦合和加氢反应,其中,Mn、Zr促进加氢的作用更显著。     

The role of carbon support morphology in the formation of catalytic layer of solid-polymer fuel cell

The Pt/C catalysts with similar morphology of active catalytic phase (platinum nanoparticles), which were deposited on the supports with different types of carbon structures (Vulkan XC-72 carbon black, Taunit carbon tubes, and Timrex HSAG-300 carbon support with graphite structure), were fabricated by the method of electrochemical dispersion. The effect of the carbon structure type on the electrocatalytic properties of Pt/C catalysts was studied in their operation in the three-electrode cell and in-service in the membrane-electrode assembly of air-hydrogen solid-polymer fuel cell. The Pt/C catalyst based on the Vulkan XC-72 carbon support showed the best performance. The anisotropic shape of Taunit carbon nanotubes and the microstructure of Timrex HSAG-300 carbon support do not allow us to form a catalytic layer with a large active platinum surface area and a structure, which provides an effective ionic transport and mass exchange near the platinum surface.     

Gas Phase Selective Catalytic Oxidation of Toluene to Benzaldehyde on V2O5-Ag2O／η-Al2O3 Catalyst

Gas phase selective catalytic oxidation of toluene to benzaldehyde was studied on V2O5-Ag2O/η-Al2O3 catalyst prepared by impregnation. The catalyst was characterized by XRD, XPS, TEM,and FT-IR. The catalytic results showed that toluene conversion and selectivity for benzaldehyde on catalyst sample No.4 (V/(V Ag)=0.68) was higher than other catalysts with different V/Ag ratios. This was attributed to the higher surface area, larger pore volume and pore diameter of the catalyst sample No.4 than the other catalysts. The XRD patterns recorded from the catalyst before and after the oxidation reaction revealed that the new phases were developed, and this suggested that silver had entered the vanadium lattice. XPS results showed that the vanadium on the surface of No.4 and No.5 sample was more than that in the bulk, thus forming a vanadium rich layer on the surface. It was noted that when the catalyst was doped by potassium promoter, the toluene conversion and selectivity for benzalde hydewere higher than those on the undoped catalyst. This was attributed to the disordered structure of V2O5 lattice of the K-doped catalyst and a better interfacial contact between the particles.     

Mono- and heterometallic carbonyl precursor based RuMo/Al2O3 catalysts: hydrodesulfurization activity and temperature programmed studies

The effects of preparation process and starting material on hydrodesulfurization (HDS) activity of alumina supported ruthenium, molybdenum and ruthenium–molybdenum hydrotreating catalysts were investigated. Conventional impregnation method and gradual gas phase adsorption were compared as a preparation route. The HDS tests showed that controlled gas phase deposition is advantageous in the preparation of the monometallic catalyst systems. The most promising HDS activity was achieved with the RuMo/Al₂O₃ catalyst prepared from binuclear organometallic complex. This suggests that the direct ruthenium–molybdenum bond in the structure of the catalyst precursor favors the formation of highly active surface phase. The oxidation and reduction behavior of the catalysts was studied by oxygen pulse chemisorption (PCO) and temperature programmed reduction (TPR). A clear relationship was observed between the method of preparation and the reactivity of the surface species.     

丙烷氨氧化V／Sb系复合氧化物催化剂的研究

考察了不同组成的Ｖ－Ｓｂ－Ｏ系复合氧化物对丙烷氨氧化的催化活性。用ＸＲＤ研究了催化剂的结构，利用程序升温方法研究了催化剂中氧的活动性和表面酸碱性，讨论了催化剂体相和表面结构与催化性能间的关系。结果表明，ＶＳｂＯ４和Ｓｂ２Ｏ４间的协同作用是影响催化活性的重要因素。     

Gas Phase Selective Catalytic Oxidation of Toluene to Benzaldehyde on V2O5-Ag2O/η-Al2O3 Catalyst

Gas phase selective catalytic oxidation of toluene to benzaldehyde was studied on V2O5-Ag2O/η-Al2O3 catalyst prepared by impregnation. The catalyst was characterized by XRD, XPS, TEM,and FT-IR. The catalytic results showed that toluene conversion and selectivity for benzaldehyde on catalyst sample No.4 (V/(V Ag)=0.68) was higher than other catalysts with different V/Ag ratios. This was attributed to the higher surface area, larger pore volume and pore diameter of the catalyst sample No.4 than the other catalysts. The XRD patterns recorded from the catalyst before and after the oxidation reaction revealed that the new phases were developed, and this suggested that silver had entered the vanadium lattice. XPS results showed that the vanadium on the surface of No.4 and No.5 sample was more than that in the bulk, thus forming a vanadium rich layer on the surface. It was noted that when the catalyst was doped by potassium promoter, the toluene conversion and selectivity for benzaldehyde were higher than those on the undoped catalyst. This was attributed to the disordered structure of V2O5 lattice of the K-doped catalyst and a better interfacial contact between the particles.     

ZrO2添加方法对CuO-ZnO-ZrO2催化剂性能的影响

研究了ZrO₂的两种加入法所得CuO-ZnO-ZrO₂催化剂对CO₂加H₂合成CH₃OH反应催化活性的影响,得到催化剂的最佳含量组成及各种操作条件下的活性规律。采用BET、XRD、TPR、XPS等手段对催化剂表面晶相组成、活性组分存在状态进行了探讨。     

Determination of the chemical composition of supported vanadium-containing oxide catalysts by the differential dissolution method

The results of the application of the stoichiographic method of differential dissolution (DD) in the determination of the chemical composition of vanadium-containing catalysts are presented. In the studied catalyst series, amounts of vanadium were deposited onto TiO₂, SiO₂, Al₂O₃, ZrO₂, and Nb₂O₅. The catalysts were prepared by the impregnation method or by the spray drying method and thermally treated at different temperatures. The DD method was used for the precise correction of the phase composition of the V₂O₅/TiO₂ catalyst samples in order to determine the nature of the active component of these catalysts and obtain the correct information on their structure using the NMR method.     

制备溶剂对NiCoB非晶态合金催化剂结构及糠醛加氢性能的影响

采用化学还原法在不同单一和复配溶剂体系中制备了一系列NiCoB非晶态合金催化剂,对其液相糠醛加氢性能进行了考察,并采用N_2吸附-脱附等温线、ICP、FE-SEM、HRTEM、XRD、XPS等手段进行了表征。结果表明,在相同反应条件下,制备溶剂的表面张力、黏度、极性大小和溶解度常数等对NiCoB非晶态合金催化剂的组成、形貌和结构及其糠醛加氢反应性能均产生重要影响。由甲醇/乙二醇复配溶剂(MEG,体积比1∶1)制备的NiCoB-MEG催化剂具有最理想的糠醛液相加氢制糠醇性能,糠醛转化率达到96.4%,糠醇选择性达到83.49%,这可归因于甲醇和乙二醇之间的协同作用促进了金属组分的分散和还原。     

Adsorption properties of Ni-Pd catalysts supported on aluminum oxide

The surface composition of Ni-Pd/Al₂O₃ catalysts has been studied using XPES and adsorption methods. The bimetallic catalysts differ from the single-metal Ni and Pd catalysts in the dispersivity of the metal phase which depends on the method of preparation and the presence of K⁺ promoter. A catalyst produced by the immersion method is strongly enriched in Pd compared with impregnated catalysts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1746–1751, August, 1991.     

In Situ Radioisotopic Study of the Active Sites of Sulfide CoMo Catalysts and the Mechanism of Thiophene Hydrodesulfurization

The mechanism of thiophene hydrodesulfurization over sulfide catalysts for hydrotreating and the effect of the catalyst composition and feed on the number, distribution, and performance of active sites were studied using ³⁵S and ³H isotopes. Based on the results of radioisotopic study, a method for systematic testing–monitoring of sulfide Co(Ni)Mo catalysts for hydrotreating is developed. The method involves the evaluation of the fraction of the active phase surface occupied by SH groups and the ratio between the concentrations of the surface SH groups and coordinatively unsaturated sites including functioning vacancies. General conditions for the formation and functioning of active sites are formulated on the basis of the monitoring data. Criteria for evaluation of the catalyst performance under conditions of hydrodesulfurization of various kinds of crude are proposed. The results of the pilot tests of commercial catalysts suggest that the criteria proposed are suitable.     

载体TiO2对Co-P非晶态合金性质的影响

用还原沉积法分别合成了纯态Co-P非晶态合金和一种新型负载非晶态合金催化剂CoP/TiO₂, 用XRD, ICP, TEM, BET和DSC等手段对催化剂的物理性质进行了表征, 比较了它们的结构、组成、形貌、表面积及热稳定性等物理性质及其对PH₃分解的催化活性. 与纯态Co-P非晶态合金比较, CoP/TiO₂具有更大的表面积和较高的热稳定性及催化活性, 这缘于TiO₂载体与催化剂的相互作用以及载体对Co-P良好的分散性能.     

制备方法对钒磷氧复合氧化物晶相和比表面积的影响

采用水相、有机相及球磨法等不同方法制备了VPO催化剂,使用BET、XRD等测试手段对VPO催化剂的比表面积、晶相结构进行了表征,研究发现水相法制备时,比表面积较小,晶相较复杂,焙烧温度升高,结晶度增加,有机相和球磨法制备时,催化剂的比表面积较大,晶相几乎为(VO)2P2O7,在超临界条件下干燥,可使所有催化剂比表面积显著增大，晶相更完善。     

改性Ni-B合金的制备及其催化糠醛加氢性能的研究

非晶态合金是一类介于晶态和无定形物质之间的特殊材料,其组成元素之间以金属键相连并在几个晶格常数范围内保持短程有序而长程无序,这种独特结构使其具有优良的催化性能,并大多被用于加氢反应例如,苯加氢制环己烷[1,2],硝基苯加氢制苯胺[3,4],环戊二烯选择加氢[5],腈类加氢[6,     

Deactivation and oxidative regeneration of modern catalysts for deep hydropurification of diesel fuel: Oxidative regeneration of IK-GO-1 catalyst

Oxidative regeneration of a deactivated IK-GO-1 catalyst was studied in removal of carbonaceous deposits and sulfur from the catalyst composition. Elemental analysis data, texture characteristics, and catalytic activities of fresh and regenerated samples were compared. Raman spectroscopy, X-ray phase analysis, electronic diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy were used to examine the structure of cobalt and molybdenum compounds entering into the composition of the catalysts.     

溶胶-凝胶法对NiO/γ-Al_2O_3催化剂在甲烷部分氧化制合成气反应中催化性能的影响(英文)

利用浸渍法和溶胶－凝胶法制备ＮｉＯ／γ－Ａｌ２Ｏ３催化剂。通过８０小时寿命实验的比较,研究了制备方法对甲烷部分氧化制合成气催化性能的影响。利用ＴＧ、ＸＰＳ、ＡＡＳ、ＴＰＲ、ＢＥＴ和ＸＲＤ等一系列表征方法考察了催化剂积碳、表面组成、Ｎｉ含量、表面积、孔体积和晶相的变化情况。结果表明,在高温氧化还原反应中,虽然利用溶胶－凝胶法制备的催化剂不能提高催化剂担体的热稳定性,但是能够提高Ｎｉ基催化剂的抗积碳和抗Ｎｉ的流失与烧结的能力。     

Co-Mg/Al类水滑石衍生复合氧化物上N2O催化分解的研究

恒定二价与三价阳离子比为3((nCo+nMg)/nAl=3), 采用共沉淀法制备不同Co含量的系列类水滑石前驱物CoxMg3-xAl-HT(x=0, 0.5, 1, 1.5, 2, 2.5, 3), 经焙烧得到其衍生复合氧化物催化剂CoxMg3-xAlO. 采用XRD、BET、TG-DSC和TPR等表征手段考察了Co含量对材料前驱物及其衍生复合氧化物组成和结构等方面的影响, 研究了系列CoxMg3-xAlO催化剂的催化N2O分解性能; 同时探讨了反应条件, 如N2O浓度、空速、O2和H2O等因素对催化剂活性的影响. 结果表明, 所有前驱物材料均能形成完整的层状水滑石结构；经高温焙烧后形成了以Co-Al尖晶石为主相的复合氧化物, 且Co掺杂有助于尖晶石相的生成； Co含量对材料的热稳定性、比表面、可还原性和催化分解活性有显著的影响；含Co复合氧化物催化材料存在两个还原峰, 还原过程为Co3+→Co2+→Co；Mg有助于提高催化剂的热稳定性；随着Co含量增加, 催化剂比表面下降, 但比表面不是影响催化剂活性的主要因素； 500 ℃焙烧后的Co2.5Mg0.5AlO催化剂具有较好的N2O催化分解活性；提高前驱物的焙烧温度导致催化剂的活性下降；N2O浓度、空速及O2对催化剂活性的影响较小, 而H2O则对催化剂的活性有较大的影响.