文献类型：期刊文献

英文题名：Leveraging the Proximity and Distribution of Cu-Cs Sites for Direct Conversion of Methanol to Esters/Aldehydes

作者：Chen, Wenyao[1];Zuo, Ji[1];Sang, Keng[1];Qian, Gang[1];Zhang, Jing[1];Chen, De[2];Zhou, Xinggui[1];Yuan, Weikang[1];Duan, Xuezhi[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway

年份：2024

卷号：63

期号：1

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20234815135009);WOS:【SCI-EXPANDED(收录号:WOS:001110149400001)】；

基金：This work was financially supported by the National Key R&D Program of China (2022YFA1503503 and 2022YFA1503504), the Natural Science Foundation of China (22038003, 22178100, 22178101, U22B20141 and 22008066), the Innovation Program of Shanghai Municipal Education Commission, the Program of Shanghai Academic/Technology Research Leader (21XD1421000), the Shanghai Science and Technology Innovation Action Plan (22JC1403800). The authors thank Dr. Xin Zhou from Ocean University of China for the help of techno-economic analysis, and Dr. Xiang Tian from Shanghai Huayi Group Co. for the help of DFT calculations. The authors thank beamline BL14W1 (Shanghai Synchrotron Radiation Facility) for the beam time and assistance in the experiments.

语种：英文

外文关键词：Esters and Aldehydes; Heterogeneous Catalysis; Methanol; One-Step Conversion; Reaction Mechanisms

摘要：Methanol serves as a versatile building-block for various commodity chemicals, and the development of industrially promising strategies for its conversion remains the ultimate goal in methanol chemistry. In this study, we design a dual Cu-Cs catalytic system that enables a one-step direct conversion of methanol and methyl acetate/ethanol into high value-added esters/aldehydes, with customized chain length and saturation by leveraging the proximity and distribution of Cu-Cs sites. Cu-Cs at a millimeter-scale intimacy triggers methanol dehydrogenation and condensation, involving proton transfer, aldol formation, and aldol condensation, to obtain unsaturated esters and aldehydes with selectivities of 76.3 % and 31.1 %, respectively. Cu-Cs at a micrometer-scale intimacy significantly promotes mass transfer of intermediates across catalyst interfaces and their subsequent hydrogenation to saturated esters and aldehydes with selectivities of 67.6 % and 93.1 %, respectively. Conversely, Cu-Cs at a nanometer-scale intimacy alters reaction pathway with a similar energy barrier for the rate-determining step, but blocks the acidic-basic sites and diverts the reaction to byproducts. More importantly, an unprecedented quadruple tandem catalytic production of methyl methacrylate (MMA) is achieved by further tailoring Cu and Cs distribution across the reaction bed in the configuration of Cu-Cs||Cs, outperforming the existing industrial processes and saving at least 15 % of production costs. An unprecedented quadruple tandem catalytic production of esters and aldehydes from methanol and methyl acetate/ethanol has been developed, allowing for customized chain length and saturation by leveraging the proximity and distribution of Cu-Cs sites. This approach has the potential to revolutionize the production of value-added methyl methacrylate (MMA), surpassing the current industrial processes to significantly lower the production costs.image