M-BTC as Efficient Catalyst for the Synthesis of Cyclic Organic Carbonates Assisted Tandem by Olefin Epoxidation and CO2 Cycloaddition

IF 2.3 4区化学 Q3 CHEMISTRY, PHYSICAL Catalysis Letters Pub Date : 2024-11-27 DOI:10.1007/s10562-024-04881-x

Ruiping Wei, Ziqi Wang, Mingzhu Yao, Rongying Xia, Huijun Liu, Lei Yang, Guanghui Ma, Lijing Gao, Guomin Xiao

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Abstract

The metal-organic frameworks (MOFs) with oxidative and acidic active sites demonstrate promising potential for tandem reactions involving olefin oxidation carboxylation. In this study, M-BTCs were synthesized via a solvothermal method, employing 1,3,5-benzenetricarboxylic acid (H₃BTC) as a ligand in combination with various metals (Mn, Co, Cu, Ni). The good thermal stability and morphology of M-BTC was verified by various characterization techniques, and its catalytic performance was evaluated for oxidative carboxylation. The catalytic activity of Mn-BTC, with Mn³⁺/ Mn²⁺as the primary oxidation site, was found to be superior in both olefin epoxidation and CO₂ cycloaddition. The effects of reaction conditions on both epoxidation of styrene and the cycloaddition reaction were investigated, respectively. Under optimal reaction conditions (epoxidation: 10 wt% Mn-BTC of styrene, 80 ℃ for 12 h; cycloaddition: 100 ℃ for 12 h with a CO₂ flow rate of 15 ml/min and tetrabutylammonium bromide (TBAB) amount of 15 mol%), a 53% yield of styrene carbonate (SC) was obtained in the assisted tandem reactions. Furthermore, cycling experiments as well as XRD and FT-IR spectra of the catalysts after use demonstrated that Mn-BTC maintained its crystal structure and retained a yield of 49% SC after three cycles. Finally, a possible mechanism for assisted tandem catalytic reaction over Mn-BTC was proposed.

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M-BTC 作为高效催化剂通过烯烃环氧化和 CO2 环加成串联合成环状有机碳酸盐

具有氧化活性位点和酸性活性位点的金属有机框架（MOFs）在涉及烯烃氧化羧化的串联反应中展现出了巨大的潜力。本研究以 1,3,5-苯三羧酸（H3BTC）为配体，结合多种金属（锰、钴、铜、镍），通过溶热法合成了 M-BTC。各种表征技术验证了 M-BTC 良好的热稳定性和形态，并评估了其氧化羧化催化性能。研究发现，以 Mn3+/ Mn2+ 为主要氧化位点的 Mn-BTC 在烯烃环氧化和 CO2 环加成反应中的催化活性都很出色。分别研究了反应条件对苯乙烯环氧化反应和环加成反应的影响。在最佳反应条件下（环氧化：10 wt% Mn-BTC 的苯乙烯，80 ℃，12 小时；环加成反应：在最佳反应条件下（环氧化：10 wt%的 Mn-BTC，80 ℃，12 h；环加成：100 ℃，12 h，CO2 流速为 15 ml/min，四丁基溴化铵（TBAB）用量为 15 mol%），辅助串联反应获得了 53% 的碳酸苯乙烯（SC）产率。此外，催化剂使用后的循环实验以及 XRD 和 FT-IR 光谱显示，Mn-BTC 保持了其晶体结构，并在三个循环后保持了 49% 的碳酸苯乙烯产率。最后，提出了 Mn-BTC 辅助串联催化反应的可能机理。

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来源期刊

Catalysis Letters 化学-物理化学

CiteScore

5.70

自引率

3.60%

发文量

327

审稿时长

1 months

期刊介绍： Catalysis Letters aim is the rapid publication of outstanding and high-impact original research articles in catalysis. The scope of the journal covers a broad range of topics in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis. The high-quality original research articles published in Catalysis Letters are subject to rigorous peer review. Accepted papers are published online first and subsequently in print issues. All contributions must include a graphical abstract. Manuscripts should be written in English and the responsibility lies with the authors to ensure that they are grammatically and linguistically correct. Authors for whom English is not the working language are encouraged to consider using a professional language-editing service before submitting their manuscripts.