Preparation of Self-Responsive Materials by Mean of Intercalation Compounds with Polymer Gels and Application to Intelligent Catalysts

聚合物凝胶插层化合物制备自响应材料及其在智能催化剂中的应用

• 批准号: 12650863
• 负责人: SHTMAZU Shogo
• 金额: $ 2.37万
• 依托单位: CHIBA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650863/
• 关键词: CLAY MINERALS; HECTORITE; TAENIOLITE; RHODIUM COMPLEXES; ASYMMETRIC HYDROGENATION; TUNING GUESTS; HOST-GUEST; MOLECULAR RECOGNITION; 自己応答性

(1) The preparation of self-responsive catalysts (intelligent catalysts) was tried by means of nano composites composed of three components, i. e., (i) structural tuning guests(STG), (ii) metal complexes as catalytic active species, and (iii) inorganic layer compounds as host.(2) <Results>Various type of host compounds were used to control the interlayer space size such as smectites (taeniolite(TN), hectorite(HT) as cation exchangers) and botallackite type compounds (nickel-zinc acetate(Ni-ZnAc) as anion exchanger). Various Rh(I) complexes are intercalated into these cationic and anionic layer compounds to prepare the Rh(I)-supported catalysts with various interlayer space sizes. Various catalytic hydrogenation reactions such as hydrogenation of dienes, alkynes, and ketones were carried out by means of the obtained catalysts to evaluate the molecular recognition. The following results were obtained : (i)<Control of interlayer space by means of STG and cation exchangers> The basal spacing of I smectites ranged from 2.51〜3.72 nm by means of STG (alkyl ammoniums) with C10, C14, and CI18. (ii)< Control of interlayer space by means of STG and cation exchangers> The basal spacing of Ni-ZnAc ranged from 2.51〜3.27 nm by means of STG (carboxylic acids) with C10, C14, and CI18. Rh-TPPTS (phosphinetribenzenesulphonate) anion was intercalated into Ni-ZnAc to prepare the supported catalysts. (iii)<Control of interlayer space by means of Rh(I) complexes with structural tuning ligands (STL)> Rh(I)-STL complexes were prepared by means of 4-alkylpyridine(CnPy) and 4,4 '-dialkyl-2,2 '-bipyridine (Cnibpy)(n=1,5,9). These Rh(I)STL complexes are intercalated into TN to give the basal spacing ranging from l.9〜2.72 nm.The activity of catalysts clearly depended on the basal spacing of the supported catalysts and these catalysts showed molecular size, regio, and chiral selectivity.The intercalation of polymer gels such as PVME was not observed due to the lack of ionized functional groups.

(1)采用三组分纳米复合材料制备自响应催化剂（智能催化剂），即(1)结构调谐客体（STG），(2)金属配合物作为催化活性物质，(3)无机层化合物作为主体。(2) <结果>采用不同类型的基质化合物控制层间空间大小，如蒙脱石（带沸石（TN）、百长石（HT）作为阳离子交换剂）和硼钛矿（醋酸镍锌（Ni-ZnAc）作为阴离子交换剂）。将不同的Rh(I)配合物插入到这些阳离子和阴离子层化合物中，制备出具有不同层间空间大小的Rh(I)负载催化剂。利用所制备的催化剂进行了多种催化加氢反应，如二烯、炔和酮的加氢反应，以评价其分子识别能力。结果表明：(1)STG和阳离子交换剂>对层间空间的控制STG（烷基铵）与C10、C14和CI18对i型蒙脱石基间距的控制范围为2.51 ~ 3.72 nm。（ii） STG和阳离子交换剂>对层间空间的控制STG（羧酸）与C10、C14和CI18对Ni-ZnAc基间距的控制范围为2.51 ~ 3.27 nm。将Rh-TPPTS（磷酸三苯磺酸钠）阴离子插入Ni-ZnAc中制备负载催化剂。（iii）<通过结构调谐配体（STL）控制层间空间的Rh(I)配合物>通过4-烷基吡啶（CnPy）和4,4 '-二烷基-2,2 '-联吡啶（cnbpy）制备了Rh(I)-STL配合物（n=1,5,9）。这些Rh(I)STL配合物插入到TN中，基间距为1.9 ~ 2.72 nm。催化剂的活性明显取决于载体的基间距，这些催化剂表现出分子大小、区域和手性选择性。由于缺乏离子化官能团，未观察到PVME等聚合物凝胶的插层。

项目成果

島津省吾: "粘土鉱物層間の化学修飾と分子認識触媒への応用"粘土科学. 40. 166-172 (2001)

Shogo Shimazu：“粘土矿物层之间的化学改性及其在分子识别催化剂中的应用”Clay Science 40. 166-172 (2001)。

S. Shimazu et al.: "Preparation of Micro- and Mesoporous Reaction Sites by the Intercalation of Metal Compkexes with Various Structural Tuning Ligands into Clays"Proceeding of The Fourth International Tokyo Conference on Advanced Catalytic Science and Tec

S. Shimazu 等人：“通过将金属络合物与各种结构调整配体插入粘土来制备微孔和介孔反应位点”第四届国际东京高级催化科学与技术会议论文集

S.Shimazu, T.Aman, Y.Sato, N.Ichikuni, T.Uematsu: "Preparation of Micro- and Mesoporous Reaction Sites by the Intercalation of Metal Complexes with Various Structural Tuning Ligands into Clays"Proceeding of The Fourth International Tokyo Conference on Adv

S.Shimazu、T.Aman、Y.Sato、N.Ichikuni、T.Uematsu：“通过将金属络合物与各种结构调节配体插入粘土来制备微孔和介孔反应位点”第四届国际东京会议论文集

S. Shimazu et al.: "Regioselective hydrogenation of dienes catalysed by palladium-aminosilane complexes grafted on MCM-41"Journal of Molecular Catalysis A : Chemical. (in press). (2002)

S. Shimazu 等人：“接枝在 MCM-41 上的钯-氨基硅烷复合物催化的二烯区域选择性氢化”《分子催化杂志 A：化学》。

S.Shimazu: "Preparation of Micro-and Mesoporous Reaction Sites by the Intercalation of Metal Complexes with Various Structural Tuning Ligands into Clays"Proceeding of The Fourth international Tokyo Conference on Advanced Catalytic Science and Technology.

S.Shimazu：“通过将金属络合物与各种结构调整配体插入粘土来制备微孔和介孔反应位点”第四届国际东京高级催化科学技术会议论文集。