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.

金属铜是丝光沸石(MOR)催化二甲醚(DME)羰化合成乙酸甲酯(MA)的最佳助剂。到目前为止，主要的反应机理表明，CO或DME的活化需要分子筛中金属官能位和B酸中心(BAS)的帮助。因此，几乎所有报道的铜改性MoR催化剂都采用浸渍或离子交换的制备方法来实现更紧密的连接。然而，铜和BAS在不同尺度上的亲和力的影响还没有得到很好的描述。在过去的一年里，我们设计并制备了不同空间组装风格的催化剂。分别采用浸渍和离子交换法制备了纳米级分子筛的铜/莫尔和铜-莫尔。将Cu/SiO_2与MoR混合、研磨、造粒，制得了Cu/SiO_2&H-MoR。对于Cu/SiO_2+H-MoR类型，在不进一步研磨的情况下，将Cu/SiO_2颗粒与H-MoR颗粒混合在一起。Cu/SiO_2//H-MoR和H-MoR//Cu/SiO_2代表了完全分离的组装方式(厘米级)。随着还原温度的升高，MA在Cu/SiO_2和H-MoR催化剂上的反应温度从1725 mm o l/(kg·h)增加到2946 mm o l/(Kgh)，但本文采用的是Cu/SiO_2和H-MoR的混合催化剂，其中金属与BAS之间的距离比前人研究的传统的Cu/SiO_2和Cu-MoR催化剂要远得多。因此，在我们的催化体系中，二甲醚羰化反应的内在机理应该与以前的所有报道都有根本的不同。

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