触媒活性サイトの空間組織が反応に及ぼす影響研究

催化活性位点空间组织对反应影响的研究

• 批准号: 22KJ1456
• 负责人: 姚 杰
• 金额: $ 1.09万
• 依托单位: University of Toyama
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2023
• 资助国家: 日本
• 起止时间: 2023-03-08 至 2024-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-22KJ1456/
• 关键词: Carbonylation; Zeolite; Spatial Assembly; Copper

Metal copper was certified as the best promoter in carbonylation of dimethyl ether (DME) to methyl acetate (MA) over mordenite (MOR) zeolite. To date, the major reaction mechanism suggested that the activation of either CO or DME needed assistance from both metal functional sites and Bronsted acid sites (BAS) in zeolites. Therefore, almost all reported Cu modified MOR catalysts employed the preparation method of impregnation or ion exchange for a closer connection. However, the impact of intimacy between copper and BAS at different scales is still not well described.In the past year, we designed and prepared catalysts with different spatial assembly styles. Cu/MOR and Cu-MOR with the distance between Cu and BAS of zeolite in nanoscale were prepared by impregnation and ion exchange respectively. The Cu/SiO2&H-MOR was prepared via mixing, grinding, and pelleting of Cu/SiO2 with MOR. For Cu/SiO2+H-MOR style, Cu/SiO2 particles and pelleted H-MOR granules were mixed without further grinding. The Cu/SiO2//H-MOR and H-MOR//Cu/SiO2 represent the completely separated assembly style (centimeter-scale). The STY of MA over Cu/SiO2&H-MOR was found to increase from 1725 to 2946 mmol/(kg h) along with raising the reduced temperature.However, here we adopted the mixture catalyst of Cu/SiO2 and H-MOR, in which the distance between the metal and BAS was much farther than the conventional Cu/MOR and Cu-MOR catalysts by former researchers. Therefore, the intrinsic mechanism of DME carbonylation in our catalytic system should be fundamentally different from all of the previous reports.

以丝光沸石（莫尔）为催化剂，研究了金属铜对二甲醚（DME）羰基化合成乙酸甲酯（MA）反应的促进作用。迄今为止，主要的反应机理表明，CO或DME的活化需要沸石中的金属功能中心和布朗斯台德酸中心（BAS）的帮助。因此，几乎所有报道的Cu改性的莫尔还原催化剂都采用浸渍或离子交换的制备方法，以使连接更紧密。然而，铜和BAS在不同尺度上的亲密度的影响仍然没有得到很好的描述。在过去的一年里，我们设计并制备了具有不同空间组装风格的催化剂。分别采用浸渍法和离子交换法制备了Cu/莫尔和Cu与分子筛BAS间距为纳米级的Cu-莫尔复合材料。将Cu/SiO2与莫尔还原剂混合、研磨、造粒，制备了Cu/SiO2& H-莫尔还原剂。对于Cu/SiO2+H-MOR类型，将Cu/SiO2颗粒和造粒的H-MOR颗粒混合而不进一步研磨。Cu/SiO2//H-MOR和H-MOR//Cu/SiO2代表完全分离的组装风格（厘米级）。在Cu/SiO_2和H-MOR催化剂上，MA的STY沿着还原温度的升高而从1725增加到2946 mmol/（kg·h），但我们采用的是Cu/SiO_2和莫尔的混合催化剂，其金属与BAS的距离远大于前人研究的Cu/莫尔和莫尔催化剂。因此，在我们的催化体系中，二甲醚羰基化反应的内在机理应该与以往的报道有根本的不同。

项目成果

A newfound ionic liquid with unprecedented activity for multiple base-catalyzed reactions

• DOI: 10.1016/j.cej.2021.131955
• 发表时间: 2022
• 期刊: Chemical Engineering Journal
• 影响因子: 15.1
• 作者: W. Deng;Jie Yao;Lei Shi;Wensheng Wei;Fei Chen;Guangwen Xu

Highly thermally stable multi-porous calcium aluminum hydrotalcite catalyst for efficient carbonate synthesis

用于高效碳酸盐合成的高热稳定性多孔钙铝水滑石催化剂

• DOI: 10.1016/j.fuel.2022.125696
• 发表时间: 2022
• 期刊: Fuel
• 影响因子: 7.4
• 作者: Deng Wenjie;Yao Jie;Shi Lei
• 通讯作者: Shi Lei

Effects of zeolite morphologies on CO conversion to aromatics via a modified Fischer-Tropsch synthesis pathway

沸石形态对通过改进的费托合成途径将 CO 转化为芳烃的影响

• DOI: 10.1002/jctb.7216
• 发表时间: 2022
• 期刊: Journal of Chemical Technology and Biotechnology
• 影响因子: 3.4
• 作者: Zhang Baizhang;Yao Jie;Wang Yang;Gao Weizhe;Kugue Yasuharu;Guo Xiaoyu;He Yingluo;Yang Guohui;Tsubaki Noritatsu
• 通讯作者: Tsubaki Noritatsu