Molecular Design of Cluster Catalysts in Micropore and Selective Activation of Alkanes

微孔团簇催化剂的分子设计及烷烃的选择性活化

• 批准号: 62470069
• 负责人: ICHIKAWA Masaru
• 金额: $ 3.84万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-62470069/
• 关键词: Cluster; Zeolite; Alkane Activation; Bimetal Catalysts; Multisite Effect; Ensemble Effect; Ligand Effect; Hydrogenolysis; クラスター; バイメタルクラスター; ゼオライト担持触媒; 合成ガス反応; 含酸素化合物合成; ヒドロホルミル化反応; 直鎖状アルコール合成; 超強酸点の化学設計

A series of metal/bimetal catalysts have been prepared from the carbonyl clusters such as Rh_<6-X>Ir_X(CO)_<16> (X=0-6) and [Fe_2Rh_4(CO)_<16>]^<2-> which were synthesized inside NaY zeolite supercages. NaY-entrapped Rh_6, Ir_6, Rh_4Ir_2, Rh_3Ir_3, and Rh_2Ir_4 crystallites derived from the carbonyl clusters have been well characterized by FTIR, ^<129>Xe NMR, and CO/H chemisorption on their metallic structure and electronic states. The results suggested that the reduced crystallites inside NaY zeolite consisted of the cluster ensemble with the controlled metal compositions and fairly stabilized through several sequence of oxidation, reduction, and alkane hydrogenolysis. As the test reactions, hydrogenlysis of n-butane and ethane, and benzene hydrogenation were conducted. It is of interest to observe the dramatic decrease of hydrogenolysis activity by four order of magnitude across the series of clusters by increasing the number of modest Ir atoms in the active Rh ensembles, while a slight enhanacement activity for the benzene hydrogenation. For butane hydrogenolysis, the smaller Rh ensembles in the bimetallic clusters gave the maximum selectivities towards the central C-C bond scission to give C_2H_6.

以NaY沸石超级笼内合成的Rh_<6-X>Ir_X(CO)_<16> (X=0-6)和[Fe_2Rh_4(CO)_<16>]^<2->等羰基簇​​制备了一系列金属/双金属催化剂。由羰基簇衍生的NaY包埋的Rh_6、Ir_6、Rh_4Ir_2、Rh_3Ir_3和Rh_2Ir_4微晶已通过FTIR、^ 129 Xe NMR和CO/H化学吸附对其金属结构和电子态进行了很好的表征。结果表明，NaY沸石内的还原微晶由具有受控金属成分的团簇集合组成，并且通过氧化、还原和烷烃氢解的几个顺序而相当稳定。作为测试反应，进行正丁烷和乙烷的氢化以及苯的氢化。有趣的是，通过增加活性 Rh 系综中适度 Ir 原子的数量，观察到一系列簇的氢解活性急剧下降四个数量级，同时苯氢化活性略有增强。对于丁烷氢解，双金属簇中较小的Rh系综对中心C-C键断裂产生C_2H_6具有最大选择性。

项目成果

L.Rao: "Characterization of Nay Entrapped Rh_6 (CO)_<16> _<13> Cluster by FTIR and EXAFS Spectroscopies and the Behavior in CO Isotopic Exchange Reaction" J.Phys.Chem.

L.Rao：“通过 FTIR 和 EXAFS 光谱表征 Nay 捕获的 Rh_6 (CO)_<16> _<13> 簇以及 CO 同位素交换反应中的行为”J.Phys.Chem。

福岡淳: "ゼオライト細孔内RhおよびRhFeバイメタルクラスタ-の構造とCO水素化触媒活性" 日本化学会誌. 561-568 (1989)

Jun Fukuoka：“沸石孔中Rh和RhFe双金属簇的结构和CO氢化催化活性”日本化学学会杂志561-568（1989）。

M. Ichikawa, L. Rao, T. Ito, A. Fukuoka: "Ensemble and Ligand Effects in Selective Alkane Hydrogenolysis Catalyzed on Well-characterized RhIr and RhFe Bimetallic Cluster inside Zeolite" Faraday Discuss. Chem. Soc.87. 321-336 (1989)

M. Ichikawa、L. Rao、T. Ito、A. Fukuoka：“沸石内良好表征的 RhIr 和 RhFe 双金属簇催化的选择性烷烃氢解中的整体和配体效应”法拉第讨论。

L. Rao, A. Fukuoka, N. Kosugi, H. Kuroda, M. Ichikawa: "Characterization of NaY Entrapped Rh_6 (CO)_<16> Cluster_<13> by FTIR and EXAFS Spectroscopies and the・Behavior in CO Isotopic Exchange Reaction" J. Rhys. Chem.

L. Rao、A. Fukuoka、N. Kosugi、H. Kuroda、M. Ichikawa：“通过 FTIR 和 EXAFS 光谱表征 NaY 捕获的 Rh_6 (CO)_<16> Cluster_<13> 以及 CO 同位素交换中的行为反应”J. Rhys. Chem。

M.Ichikawa: "Bimetallic ClusterーCerived Heterogeneous Catalysisーーー Heterogeous Twoーsite Activation of CO in Syngas Convrsion to Oxygenatesーーー" POLYHEDRON. 7. 2351-2367 (1988)

M.Ichikawa：“双金属簇衍生的多相催化 - 合成气转化为含氧化合物中 CO 的多相活化”POLYHEDRON。 7. 2351-2367 (1988)