Thermal Study of the Cr-Mo-O System in Air

The phase diagram of the ternary system Cr-Mo-O in air was established from the results of thermal analysis of mixtures with different initial CrO3 to MoO3 ratios. It was found that MoO3 did not take any chromium oxide into solid solution. The presence of Cr2O3 destabilized MoO3 causing it to decompose to MoO2 in the temperature range 723-958 K depending on the initial Cr/Mo ratio. The decomposition of pure MoO3 MoO2 did not occur in air at any temperature. However, this decomposition took place through the formation of the compound Cr2O3·3MoO3(ss) and its decomposition to Cr2O3·3MoO2(ss). The latter compound has never been reported before and the X-ray data for this compound are given. The previously reported catalytic activity of Cr2O3·3MoO3(ss), at high temperatures, is presumably due to its reduction to Cr2O3·3MoO2(ss). This revised version was published online in July 2006 with corrections to the Cover Date.     

超声波辅助Ru-B非晶态合金常压催化肉桂醛加氢制备肉桂醇

采用KBH₄化学还原法制备了超细Ru-B非晶态合金催化剂。Ru-B催化剂在肉桂醇液相常压加氢中显示出较高的肉桂醇选择性。在加氢过程中使用超声辐射能大大提高反应速率而肉桂醇的选择性几乎保持不变。加氢速率随着超声频率或超声时间的增加而增加。通过XRD、XPS、TEM、BET和ICP等各种表征手段，简要研究了超声辐射对Ru-B催化剂结构和电子特征的影响。同时，还讨论了超声对肉桂醛选择性加氢制肉桂醇催化性能的促进作用。     

催化裂化USY／ZnO／Al2O3脱硫添加剂的高温水热失活

 对USY／ZnO／Al2O3汽油催化裂化脱硫添加剂经高温水热老化处理前后的脱硫性能进行了考察，发现老化后添加剂的脱硫性能大幅度下降．采用XRD和IR等技术对USY／ZnO／Al2O3添加剂在高温和高温水热条件下失活的原因进行了研究．结果表明，在高温下，ZnO可与USY沸石中的铝发生固相反应生成ZnAl2O4尖晶石，从而造成USY晶体结构崩塌，转变成无定形状态．在ZnO含量较高的条件下，ZnO可继续与USY晶体结构崩塌后生成的无定形的硅和铝的氧化物反应，生成Zn2SiO4硅锌矿和ZnAl2O4尖晶石结构．这一方面使添加剂失去了可形成硫化物吸附中心的ZnO，另一方面破坏了硫化物的裂化活性组分USY，从而造成添加剂脱硫性能下降甚至失去脱硫活性．ZnO对USY的破坏作用主要与温度有关．在USY／ZnO／Al2O3体系中，ZnO被ZnO与Al2O3之间形成的锌铝尖晶石膜固定并与USY隔离，单纯的高温条件对添加剂的破坏不显著，而水蒸气可以促进ZnO的移动，有利于ZnO与USY的接触，因此在高温和有水蒸气存 在的条件下添加剂的结构易遭到破坏．     

New palladium nanoclusters. Synthesis,structure, and catalytic properties

The reduction of palladium(ii) carboxylates Pd₃(OCOR)₆ (R = Me, Et, CHMe₂, CMe₃) with hydrogen in alcohol solutions containing 1,10-phenanthroline (phen) and subsequent oxidation with oxygen gave new palladium nanoclusters, mainly particles with a nearly spherical metal core and an average size of 18 . Based on elemental analysis, NMR, X-ray photoelectron spectroscopy, and EXAFS, nanoclusters were described by the idealized formula Pd₁₄₇phen₃₂O₆₀(OCOR)₃₀. The specimens contained up to 25% smaller 55-atomic Pd clusters with a 10 metal core. New nanoclusters catalyze hydrogenation of alkynes and alkenes, reduction of nitriles with formic acid, oxidation of aliphatic and benzylic alcohols, oxidative esterification of ethylene and propylene, and disproportionation of benzyl alcohol into toluene and benzaldehyde.     

A Novel Cu-Mo／ZSM-5 Catalyst for NOx Catalytic Reduction with Ammonia

The Cu-Mo/ZSM-5 catalysts with different Cu/Mo ratios were prepared by wet impregnation method, and their catalytic performance for selective catalytic reduction of NOx was studied. The results showed that Cu-Mo/ZSM-5 is a very effective catalyst for NOx catalytic reduction with ammonia, especially when Cu/Mo molar ratio is about 1.5. It not only exhibited the extremely high catalytic activity, but also showed good stability for 02. The bulk phase structure of Cu-Mo/ZSM-5 catalysts was determined by XRD technique, and the results indicated that there is a maximum dispersion for Cu species when Cu/Mo molar ratio is 1.5, and an interaction between Cu and Mo along with HZSM-5 may be present in Cu-Mo/ZSM-5, which may possibly result in a special structure favorable for the catalytic reduction of NOx over Cu-Mo/ZSM-5 catalyst.     

铈杂多配离子-水滑石超分子层柱材料ZnAl-Ce(PMoV)2的插层组装、表征及催化性能

以十四酸根阴离子柱撑Zn-Al水滑石Zn0.77Al0.22(OH)2.0.22C13H27COO.0.81 H2O(记为ZnAl-14A)为预撑前体,在水溶液中用离子交换法将以2∶17缺位杂多酸根离子(P2Mo16VO61)11-记为(P Mo V)为配体的稀土杂多配阴离子Ce(P2Mo16VO61)219-(记为Ce(PMoV)2)插层组装到水滑石层板间,合成了一种具有大的层间距(3.37 nm)的超分子插层材料Zn0.77Al0.23(OH)2.0.0105[Ce(P1.9Mo15.7V1.1O61)2].0.011C13H27COO.0.83H2O(记为ZnAl-Ce(PMoV)2)。用ICP,IR,XRD和DTA对产物的组成和结构进行了表征。结果表明,该产物中Ce(PMoV)2配阴离子沿其长轴垂直于层板的方向分布于水滑石层间;产物具有规整的层状结构和热稳定性;产物对乙酸与正丁醇的酯化反应,二甘醇的脱水-环化反应和H2O2氧化环己烷的反应有良好的催化性能,且易于回收重复使用。     

Synthesis of (trichloromethyl)organosilanes by catalytic decarboxylation of (trichloroacetoxy)organosilanes

A method for preparing (trichloromethyl)organosilanes by the catalytic decarboxylation of the corresponding trichloroacetoxysilanes RMe₂SiOC(O)CCl₃ (R = Me, ClCH₂, Ph, Me₃Si, and H) has been developed. The method involves heating the starting compounds without a solvent in the presence of a catalyst (quaternary ammonium salts or potassium salts with the addition of crown ethers). Tertiary amines (Et₃N, Bu₃N) catalyze this reaction only when heating is carried out in donor aprotic solvents (THF, acetonitrile) in the presence of oxygen. Thermal decomposition of (trichloroacetoxy)organosilanes, in contrast to catalytic decarboxylation, begins at a higher temperature and yields a mixture of products.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 150–153, January, 1995.     

催化褪色光度法测定痕量铁--Fe(Ⅲ)+亚甲基蓝+过氧化氢体系

研究了在硫酸介质中,微量铁(Ⅲ)催化过氧化氢氧化亚甲基蓝的褪色反应,建立了测定痕量铁方法.灵敏度为8.0×10-8g/mL,线性范围为0～1.000 0g/mL,用于自来水中铁的测定,结果与实际接近,相对标准偏差为0.67%.     

Complete Oxidation of Methane over Palladium Supported on Alumina Modified with Calcium,Lanthanum,and Cerium Ions

The activity and thermal stability of Pd/Al_2O_3 and Pd/(Al_2O_3 MO_x)(M=Ca,La,Ce) palladium catalysts in the reaction of complete oxidation of methane are presented in this study.The catalyst supports were prepared by sol-gel method and they were dried either conventionally or with supercritical carbon dioxide.Then they were impregnated with palladium nitrate solution.The catalysts with unmodified alumina had a high surface area.The activity and thermal stability of the alumina- supported catalyst was also very high.The introduction of calcium,lanthanum,or cerium oxide into alumina support caused a decrease of the surface area in the way dependent on the support precursor drying method.These modifiers decreased the activity of palladium catalysts,and they required higher temperatures for the complete oxidation of methane than unmodified Pd/Al_2O_3.The improvement of the palladium activity by lanthanum and cerium support modifier was observed only at low temperatures of the reaction.     

LaDAIY型沸石的裂解活性和抗氮性能

采用脉冲微反技术,以含吡啶的正庚烷为原料,考察了LaDAlY型沸石的裂解和抗氮性能。结果表明,LaDAlY型沸石的裂解与抗氮性能均优于其母体样品DAlY。结合NH_3-TPD的数据,讨论了酸性与裂解和抗氮性能之间的关系,对吡啶中毒的机理进行了探讨。