Dual-engine-driven synthesis of unsaturated esters over channel-expanding Cu–Cs catalysts

This study presents a one-step catalytic synthesis of unsaturated esters (methyl acrylate, MA; methyl methacrylate, MMA) from methanol (MeOH, C1 source) and methyl acetate (MAc) <i>via</i> a Cu-Cs dual-engine-driven (DED) system that integrates four sequential steps-dehydrogenation, aldol condensation, hydrogenation, and secondary aldol condensation. The Cu-engine facilitates proton transfer by capturing protons during MeOH dehydrogenation and donating them in methyl acrylate (MA) hydrogenation, while the Cs-engine activates saturated esters for formaldehyde-mediated aldol condensation. Through systematic optimization of Cu loading methods, deposition sequences, and Cu/Cs ratios, we developed a silicon carrier channel-expanding strategy, enlarging mesopores from 14 nm to 20 nm (30% specific surface area extension) <i>via</i> copper phyllosilicate-induced corrosion. Catalytic performance hinges on balanced medium-strength acid-base sites, a 10 : 7 Cs/Cu ratio, and sequential Cu/Cs loading <i>via</i> the ammonia evaporation method. The optimized 10Cs/7Cu/Q10 catalyst, combined with a downstream Cs-Al/Q10 system, achieves 64.0% unsaturated ester selectivity (55.3% MeOH and 59.8% methyl acetate conversion). This work establishes a design framework for efficient Cu-Cs catalysts in one-step ester synthesis, emphasizing pore engineering, acid-base synergy, and dual-site cooperativity.

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Publication Details

Journal
Chemical Science
Published
2025-01-01
DOI
https://doi.org/10.1039/d5sc02896e
Citations
2
Primary Topic
Innovative Microfluidic and Catalytic Techniques Innovation
Type
article
Field-Weighted Citation Impact
1.35

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article

Dual-engine-driven synthesis of unsaturated esters over channel-expanding Cu–Cs catalysts

Zhixin Yu, Wenjie Xiang, Bo Wang, Tao Xing et al.
2 citations
Chemical Science
Innovative Microfluidic and Catalytic Techniques Innovation
1.35
article

Dual-engine-driven synthesis of unsaturated esters over channel-expanding Cu–Cs catalysts

Zhixin Yu, Wenjie Xiang, Bo Wang, Tao Xing, Hao Huang, Lishu Shao, Noritatsu Tsubaki, Chufeng Liu, Guangbo Liu, Guohui Yang, Shuhei Yasuda, Pei‐Pei Zhang, Qiang Liu, Zhihao Liu, Tao Li, Yitong Han, Jiaqi Fan, Kangzhou Wang, Weizhe Gao, Jiancai Sui
article en
2 citations

Abstract

This study presents a one-step catalytic synthesis of unsaturated esters (methyl acrylate, MA; methyl methacrylate, MMA) from methanol (MeOH, C1 source) and methyl acetate (MAc) <i>via</i> a Cu-Cs dual-engine-driven (DED) system that integrates four sequential steps-dehydrogenation, aldol condensation, hydrogenation, and secondary aldol condensation. The Cu-engine facilitates proton transfer by capturing protons during MeOH dehydrogenation and donating them in methyl acrylate (MA) hydrogenation, while the Cs-engine activates saturated esters for formaldehyde-mediated aldol condensation. Through systematic optimization of Cu loading methods, deposition sequences, and Cu/Cs ratios, we developed a silicon carrier channel-expanding strategy, enlarging mesopores from 14 nm to 20 nm (30% specific surface area extension) <i>via</i> copper phyllosilicate-induced corrosion. Catalytic performance hinges on balanced medium-strength acid-base sites, a 10 : 7 Cs/Cu ratio, and sequential Cu/Cs loading <i>via</i> the ammonia evaporation method. The optimized 10Cs/7Cu/Q10 catalyst, combined with a downstream Cs-Al/Q10 system, achieves 64.0% unsaturated ester selectivity (55.3% MeOH and 59.8% methyl acetate conversion). This work establishes a design framework for efficient Cu-Cs catalysts in one-step ester synthesis, emphasizing pore engineering, acid-base synergy, and dual-site cooperativity.

Chemical ScienceVol. 16(28)
Central South University of Forestry and Technology (CN), Central South University (CN), Shaoxing University (CN), Chinese Academy of Sciences (CN), Ningxia University (CN), Dalian University of Technology (CN), Dalian University (CN), Advanced Technology & Materials (China) (CN), Shandong Lianxing Energy Group (China) (CN), Qingdao Institute of Bioenergy and Bioprocess Technology (CN), University of Toyama (JP)
Natural Science Foundation of Hunan Province, Science and Technology Program of Hunan Province, Japan Science and Technology Agency
Affordable and clean energy
Openalex Percentile: Top 19%
Innovative Microfluidic and Catalytic Techniques Innovation
1.35
DOIOpen Access PDFOpenAlex
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