摘要
金属有机框架(MOFs)材料由于具有酸性和表面结构可调控的特点被广泛应用于多相催化反应.本文设计并合成出一种含金属Co的梭形双金属MOF材料(ZnCo-MOFs),其可直接用于常规水热反应促进双烯烃空气环氧化反应,解决了双烯烃使用常规水热法反应困难的问题.利用X射线衍射(XRD)、扫描电子显微镜(SEM)和X射线光电子能谱(XPS)等手段表征了该材料.ZnCo-MOFs能够在无还原剂和引发剂的情况下催化双烯烃空气环氧化反应,相比单烯烃其效率明显提升.以N,N-二甲基甲酰胺(DMF)作为反应溶剂,仅90℃水浴搅拌条件下反应5 h,双烯烃环辛烯和苯乙烯的转化率分别达97.0%和98.8%,环氧选择性分别为98.4%和92.7%.该催化剂在多次循环使用后依然没有失活,具有良好的循环稳定性.
Metal-organic frameworks(MOFs),renowned for their adjustable acidity and surface architecture,have garnered significant attention in the realm of heterogeneous catalysis.The present study introduces the design and synthesis of the cobalt-incorporated,shuttle-shaped bimetallic MOF that facilitates the air epoxidation of mixed bi-olefins under water bath heating conditions,effectively overcoming the challenges of bi-olefins reactions under water bath heating.The synthesized material was comprehensively characterized through X-ray diffraction(XRD),scanning electron microscopy(SEM),and X-ray photoelectron spectroscopy(XPS).The cobalt-containing MOFs exhibited the unique capability to catalyze the air epoxidation of bi-olefins in the absence of reducing agents or initiators,achieving a marked enhancement in efficiency when compared to the epoxidation of mono-olefin.N,N-dimethyl formamide(DMF)as the solvent and in a simple water bath with magnetic stirring at 90℃for 5 h,the material demonstrated excellent conversion of 97.0%and 98.8%,respectively,for the mixture of cyclooctene and styrene;concurrently,their epoxide selectivities were found to be 98.4%and 92.7%,respectively.Furthermore,the catalyst has not been deactivated after being recycled for many times,which indicated the good cycle stability of the catalyst.
作者
张望
鲁新环
董妍红
郭昊天
严姗
周丹
夏清华
ZHANG Wang;LU Xinhuan;DONG Yanhong;GUO Haotian;YAN Shan;ZHOU Dan;XIA Qinghua(Hubei Key Laboratory for Precision Synthesis of Small Molecule Pharmaceuticals,Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules,Hubei University,Wuhan 430062,China)
出处
《高等学校化学学报》
北大核心
2025年第4期45-53,共9页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:22072038,22272045)
药物合成与优化湖北省重点实验室开放项目(批准号:ZD202302)
小分子原料药精准制造湖北省重点实验室开放基金项目(批准号:HKLB2414)资助。
关键词
梭形含钴金属有机框架材料
协同催化
双烯烃
空气环氧化
Shuttle-shaped cobalt-containing MOFs material
Synergistic catalysis
Bi-olefins
Air epoxidation
作者简介
联系人:鲁新环,女,博士,教授,主要从事多孔材料开发及有机催化方面的研究.E⁃mail:xinhuan 003@aliyun.com;联系人:夏清华,男,博士,教授,主要从事多孔材料开发及有机催化方面的研究.E-mail:xiaqh 518@aliyun.com。
