Development of Nanoporous Material-based Heterogeneous Catalysts for Metathesis

纳米孔材料基复分解多相催化剂的开发

• 批准号: 16360399
• 负责人: ONAKA Makoto
• 金额: $ 9.73万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-16360399/
• 关键词: mesoporous alumina; rhenium oxide; methyltrioxorhenium; olefin metathesis; functionalized olefin; acidic support; 不均一系メタセシス触媒; ルイス酸修飾; 塩化亜鉛; 不均一系触媒; 非極性オレフィン; 環境調和型化学合成; Lewis酸性; ナノ空間; 細孔径分布

It was found that mesoporous alumina-supported rhenium oxide (ReO_3/mesoAl_2O_3) had higher catalytic efficiency for the metathesis of simple olefins such as 1-octene and 6-tetradecene without double bond-migration, but that ReO_3/mesoAl_2O_3 was inactive toward olefins having a polar functional group such as ester and ketone.Based on the precedent report that methyltrioxorhenium (MTO) loaded on an acidic support, silica-alumina, showed efficient catalytic activity for the metathesis of olefins with such a polar functional group, in this study mesoporous materials such as mesoporous silica and mesoporous alumina were chemically acidified, and the catalytic activity for the metathesis of functionalized olefins was investigated by using a combination of the acidic mesoporous supports and methyltrioxorhenium. It was revealed that the more acidic the mesoporous support was, the higher catalysis for the metathesis was realized.The mesoporous support can discriminate the molecule sizes of reactant and product olefins since the support has a nanometer-sized homogeneous pores. Therefore, it is expected that the newly developed heterogeneous catalyst system (MTO/acidified mesoporous support) gives us shape-selective metathesis which has not been performed so far.

结果发现,介孔氧化铝负载氧化铼(ReO_3/mesoAl_2O_3)对1-辛烯、6-十四碳烯等简单烯烃复分解反应具有较高的催化效率,且无双键迁移,但ReO_3/mesoAl_2O_3对无双键迁移的烯烃不活泼。极性官能团，例如酯和酮。根据先前的报道，负载在酸性载体二氧化硅-氧化铝上的甲基三氧铼（MTO）对具有极性官能团的烯烃复分解表现出高效的催化活性，在本研究中，介孔二氧化硅和介孔氧化铝等介孔材料被化学酸化，并且催化活性通过使用酸性介孔载体和甲基三氧铼的组合研究了官能化烯烃的复分解反应。结果表明，介孔载体的酸性越高，对复分解反应的催化作用就越高。由于介孔载体具有纳米尺寸的均匀孔，因此可以区分反应物和产物烯烃的分子大小。因此，新开发的多相催化剂体系（MTO/酸化介孔载体）有望为我们带来迄今为止尚未实现的择形复分解。

项目成果

Sulfated Mesoporous Alumina : A Highly Effective Solid Strong Base Catalyst for the Tishchenko Reaction in Supercritical Carbon Dioxide

硫酸化介孔氧化铝：用于超临界二氧化碳中 Tishchenko 反应的高效固体强碱催化剂

• 发表时间: 2006
• 作者: T.Seki; M.Onaka
• 通讯作者: M.Onaka

ANew Heterogeneous Olefin Metathesis Catalyst Composed of Rhenium Oxide and Mesoporous Alumina

氧化铼和介孔氧化铝组成的新型多相烯烃复分解催化剂

• 发表时间: 2004
• 作者: T. Oikawa; P. Ookoshi; T. Tanaka; T. Yamamoto; M. Onaka
• 通讯作者: M. Onaka

A new heterogeneous olefin metathesis catalyst composed of rhenium oxide and mesoporous alumina

氧化铼和介孔氧化铝组成的新型非均相烯烃复分解催化剂

• DOI: 10.1016/j.micromeso.2004.04.026
• 发表时间: 2004-09-20
• 期刊: Microporous and Mesoporous Materials
• 影响因子: 5.2
• 作者: T. Oikawa;T. Ookoshi;Tsunehiro Tanaka;Takashi Yamamoto;M. Onaka
• 通讯作者: M. Onaka

Lewis Acid-Modified Mesoporous Alumina : A New Catalyst for Methyltrioxorheniumu in Metathesis of Olefins Bearing Functional Groups

路易斯酸改性介孔氧化铝：带有官能团的烯烃复分解甲基三氧铼的新催化剂

• 发表时间: 2007
• 作者: Oikawa; T; Masui; Y; Tanaka; T; Chujo; Y; Onaka;M
• 通讯作者: M

固体酸・塩基触媒研究の新しい展開

固体酸碱催化剂研究新进展

• 发表时间: 2005
• 作者: 尾中 篤; 關 祐威; 増井洋一
• 通讯作者: 増井洋一