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An ionic liquid in Core-shell structure: Halogen-free, metal-free bifunctional catalyst for olefin epoxidation and CO2 cycloaddition
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Yuan, Jingbo
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Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China

Meng, Haoyu
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Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China

Li, Yanan
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Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China

Liu, Ying
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Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China

Wang, Yi
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Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China

Liu, Jia
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Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China

Zhou, Zheng
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Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China
机构:
[1] Nanjing Univ, Sch Chem & Chem Engn, Nanjing 210093, Peoples R China
基金:
中国国家自然科学基金;
关键词:
Imidazole;
Heterogeneous;
Oxidation;
Cycloaddition;
CYCLIC CARBONATES;
D O I:
10.1016/j.jcou.2024.102906
中图分类号:
O6 [化学];
学科分类号:
0703 ;
摘要:
We synthesized a core-shell resin structure with abundant architecture and excellent thermal stability through polymerization. Imidazole ionic liquid with varying carbon chain lengths was immobilized on the surface, resulting in the preparation of metal-free, halogen-free core-shell catalysts with different carbon chain lengths via HCO3- 3- exchange. Characterization using FT-IR, XPS, and various techniques revealed the exceptional performance of our synthetic catalyst in terms of its internal structure. After extensive experimentation, we discovered that the synthesized catalyst exhibits dual functionality for epoxidation and CO2 2 cycloaddition reactions without requiring solvents or co-catalysts. The epoxidation system demonstrated remarkable conversion rates and selectivity while also exhibiting strong recyclability in heterogeneous reactions, according to kinetic parameters, the reaction order of styrene, TBHP and catalyst during epoxidation is approximately 1, the reference factor for this reaction was calculated to be 6.7x109 9 (L2 center dot mol-2 center dot min- 2 center dot mol- 2 center dot min- 1 ), with an activation energy of 48.9 kJ/mol obtained from analyzing reaction rates at different temperatures. In the CO2 2 cycloaddition reaction, our catalyst exhibited an advantage in catalyzing ring-opening reactions, achieving a conversion rate of 95 % for styrene oxide within six hours along with over 99 % selectivity towards cyclic carbonate formation. It is suggested that the epoxide reaction is carried out in steps, and it is inferred that the catalyst PS-ImC4HCO3 4 HCO 3 and TBHP are produced into peroxy intermediate active species TBA and HCO4, 4 , and the reaction between HCO4- 4- and styrene is the determination step of the total reaction. The reaction rate constant k=0.009 of the absolute step is calculated based on the global optimization algorithm
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页数:12
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Doyle, Abigail G.
.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,
2021, 143 (38)
:15873-15881

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Borden, Meredith A.
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Princeton Univ, Dept Chem, Princeton, NJ 08544 USA Princeton Univ, Dept Chem, Princeton, NJ 08544 USA

Steiman, Talia J.
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Princeton Univ, Dept Chem, Princeton, NJ 08544 USA Princeton Univ, Dept Chem, Princeton, NJ 08544 USA

Wang, Lucy S.
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Princeton Univ, Dept Chem, Princeton, NJ 08544 USA Princeton Univ, Dept Chem, Princeton, NJ 08544 USA

Parasram, Marvin
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Princeton Univ, Dept Chem, Princeton, NJ 08544 USA Princeton Univ, Dept Chem, Princeton, NJ 08544 USA

Doyle, Abigail G.
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Princeton Univ, Dept Chem, Princeton, NJ 08544 USA
Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA Princeton Univ, Dept Chem, Princeton, NJ 08544 USA