Development of novel solid acid catalyst based on polyanion nanosheets

基于聚阴离子纳米片的新型固体酸催化剂的研制

• 批准号: 15360427
• 负责人: HARA Michikazu
• 金额: $ 9.54万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15360427/
• 关键词: solid-acid catalysts; cation-exchangeable layered metal oxides; nanosheets; amorphous carbon; Bronsted acid sites; sulfonic acid groups; 固体酸触媒; エステル化反応; 加水分解反応; 架橋型水酸基; 酸触媒反応; 固体酸

Two-dimensional metal oxide sheets in cation-exchangeable layered metal oxides such as HTiNbO_5 and HNb_3O_8 were examined as solid-acid catalysts. Exfoliation of HTiNbO_5 and HNb_3O_8 in aqueous solutions formed colloidal single-crystal TiNbO_5 and Nb_3O_8 nanosheets, precipitating under an acidic condition to form aggregates of the nanosheets. Although esterification of acetic acid, cracking of cumene and dehydration of 2-propanol were not catalyzed by original layered metal oxides because of the narrow interlayer distance, which prevents the insertion of organic molecules, the nanosheet aggregates functioned as strong solid acid catalysts for the reactions. NH_3 temperature-programmed desorption and ^1H magic-angle spinning nuclear magnetic resonance spectroscopy revealed that these nanosheet aggregates have strong Bronsted acid sites due to Nb^<5+> (or Ti^<4+>)-(OH)-Nb^<5+>.We also found that amorphous carbon composed of small graphen sheets with high density of sulfonic acid groups function as a replacement for sulfuric acid catalyst. The material prepared from inexpensive starting materials has high thermal and chemical stability.

将可阳离子交换的层状金属氧化物（例如HTiNbO_5和HNb_3O_8）中的二维金属氧化物片作为固体酸催化剂进行了研究。 HTiNbO_5和HNb_3O_8在水溶液中剥离形成胶体单晶TiNbO_5和Nb_3O_8纳米片，在酸性条件下沉淀形成纳米片的聚集体。虽然原始层状金属氧化物由于层间距离窄而无法催化乙酸的酯化、异丙苯的裂解和2-丙醇的脱水，这阻碍了有机分子的插入，但纳米片聚集体充当了反应的强固体酸催化剂。 NH_3程序升温脱附和^1H魔角旋转核磁共振波谱表明，这些纳米片聚集体由于Nb^<5+>（或Ti^<4+>）-(OH)-Nb^而具有强布朗斯台德酸位点<5+>.我们还发现由具有高密度磺酸基团的小石墨烯片组成的无定形碳可作为硫酸催化剂的替代品。由廉价原材料制备的材料具有高热稳定性和化学稳定性。

项目成果

A.Takagaki, M.Sugisawa, J.N.Kondo, M.Hara, K.Domen, S.Hayashi: "Exfoliated Nanosheets as a New Strong Solid Acid Catalyst"Journal of the American Chemical Society. 104(4). 780-785 (2003)

A.Takagaki、M.Sugisawa、J.N.Kondo、M.Hara、K.Domen、S.Hayashi：“剥离纳米片作为新型强固体酸催化剂”美国化学会杂志。

A carbon material as a strong protonic acid

• DOI: 10.1002/anie.200453947
• 发表时间: 2004-01-01
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Hara, M;Yoshida, T;Domen, K
• 通讯作者: Domen, K

M.Hara, et al.: "To_3N_5 and TaON Thin Films on TaFoil"Journal of Physical Chemistry B. 107(48). 13441-13445 (2003)

M.Hara 等人：“TaFoil 上的 To_3N_5 和 TaON 薄膜”物理化学杂志 B. 107(48)。

A.Ishikawa, A.Yamada, T.Takata, J.N.Kondo, M.Hara, H.Kobayashi, K.Domen: "Novel Synthesis and Photocatalytic activity of Oxysulfide"Chemistry of Materials. 15(23). 4442-4446 (2003)

A.Ishikawa、A.Yamada、T.Takata、J.N.Kondo、M.Hara、H.Kobayashi、K.Domen：“硫氧化物的新颖合成和光催化活性”材料化学。

無機ナノシートの科学と応用 ナノシートの固体酸触媒への応用(黒田一幸,佐々木高義監修)

无机纳米片的科学与应用纳米片在固体酸催化剂中的应用（黑田和之和佐佐木贵佳指导）

• 发表时间: 2005
• 作者: 高垣敦;原亨和;林繁信;堂免一成
• 通讯作者: 堂免一成