Molecular beams and model catalysis: activity and selectivity of specific reaction centers on supported nanoparticles.

Reaction kinetics on nanometer-scale particles are different from those on extended surfaces of bulk materials. This fact has been utilized for a long time to empirically maximize the performance of heterogeneous catalysts, but the understanding of the underlying effects is poor at the microscopic level. Modern molecular beam-based methods, however, allow us to derive very detailed kinetic information on catalytically active surfaces. In combination with structurally highly controlled model catalysts, microscopic insights into the activity and selectivity of specific reaction centers on catalyst nanoparticles can be obtained. This combined approach is illustrated through simple model reactions.     

甲醇催化分解动力学之研究

甲醇的裂解产物为H_2与CO,故甲醇被视为一种方便、安全的贮氢材料,可作为汽油的代用燃料;其裂解气作为保护气氛可广泛应用于热处理工业。甲醇裂解有两种方法,高温热裂解(约930℃)与低温催化裂解(约300℃)由于低温催化裂解有诸多优点,在工业上的应用正在发展。     

铁(Ⅲ)-柠檬酸盐配合物光解引发橙黄Ⅱ的脱色

介绍了金属卟啉化合物的结构、种类及其应用，综述了金属卟啉化合物对烷烃的仿生催化氧化研究进展。运用金属卟啉仿生催化空气氧化环己烷制备环己酮技术，使得停留在实验室研究水平的金属卟啉仿生催化烷烃空气氧化进入了工业化生产。     

含锆层柱蒙脱石对1,2,4三甲基苯歧化反应的催化作用

用离子共聚法合成了硅锆层柱蒙脱石（ＳｉＺｒＰＩＬＭ）和铁锆层柱蒙脱石（ＦｅＺｒＰＩＬＭ），考察了它们对１，２，４三甲基苯（１，２，４ＴｒＭＢ）歧化反应的催化性能．１，２，４ＴｒＭＢ在催化剂样品上可发生歧化反应和异构化反应，歧化反应选择性达８０％以上．随着催化剂预处理温度的提高，１，２，４ＴｒＭＢ转化率下降，歧化反应选择性和四甲基苯（ＴｅＭＢ）中１，２，４，５ＴｅＭＢ含量则升高．催化剂对１，２，４ＴｒＭＢ歧化反应有择形催化作用，１，２，４，５ＴｅＭＢ和间二甲苯、邻二甲苯为主要产物，并且其含量偏离其热力学平衡组成，ＴｅＭＢ中１，２，４，５ＴｅＭＢ的含量在８５％以上．     

Vanadyl salen complexes covalently anchored to an imidazolium ion as catalysts for the cyanosilylation of aldehydes in ionic liquids

Two vanadyl salen complexes having peripheral styryl substituents have been reacted with 1-methyl-3-(3-mercaptopropyl)-imidazolium chloride using azoisobutyronitrile as radical initiator. The resulting compounds contain at the same time a vanadyl salen complex and one imidazolium cation. In agreement with the expectations in view of their structure, these compounds were insoluble in conventional organic solvents, but completely miscible in imidazolium ionic liquids. These vanadyl salen complexes bonded to an imidazolium cation are highly active and reusable catalysts for the cyanosilylation of aldehydes. Moderate enantiomeric excesses were obtained using the chiral version of this complex.     

Chiral diphosphine ligands based on camphor: synthesis and applications in asymmetric hydrogenations

The synthesis of a novel class of atropisomer chiral diphosphine ligands with a bornene framework is described. The new ligands showed in Rh catalyzed asymmetric hydrogenation of α- and β-enamides very high ee’s (more than 99%).     

ADVANCES IN STUDY OF A NEW CLASS OF PILLARED LAYERED MICROPOROUS MATERIALS?¤?¤POLYOXOMETALATE-TYPE HYDROTALCITE-LIKE CATALYSTS

In the present paper, on the basis of our work. advances in study of the catalysts of polyacid-type hydrotalcite-like are reported and reviewed. Using polyoxometalates (POM) as pillaring species and layered double hydroxides (LDH) as host matter, a new class of catalytic materials, LDHPOM, has been synthesized by five different methods. Their acidic and oxidative catalytic properties have been investigated by several research groups. The above mentioned information is given in this review.     

N－烷基吡咯烷酮的合成

Ｎ－烷基吡咯烷酮的合成王锡臣，张颂培，祝钧（北京轻工业学院化工系北京１０００３７）关键词烷基吡咯烷酮，固－液相转移催化，合成Ｎ－烷基吡咯烷酮可用作香波增稠剂，染发烫发调理剂，啤酒、葡萄酒中多酚洁净化剂和洗涤去渍剂等［１］，其合成一般采用吡咯烷酮Ｎ－烷...     

Composition catalysts of ethylbenzene oxidation based on bis(acetylacetonato)nickel(ii) and phase transfer catalysts as ligands 1. Macrocyclic polyethers

The addition of the macrocyclic polyether 18-Crown-6 (18C6) increases the selectivity of oxidation of ethylbenzene to -phenylethylhydroperoxide (PEH) in the presence of Ni(acac)₂. The initial oxidation rate, selectivity and degree of conversion of ethylbenzene to PEH are greater than those catalyzed by Ni(acac)₂ only. The efficiency of the macrocyclic ligand as an activator of Ni(acac)₂ exceeds that of monodentate donor ligands. The high selectivity of the process is due to both the primary Ni(acac)₂ · 18C6 complexes and the products of their transformation in the course of oxidation. The mechanism of ethylbenzene oxidation catalyzed by Ni(acac)₂ · 18C6 complexes is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1406–1411, August, 1994.