物理化学学报2023，Vol.39Issue(11)：95-102,8.DOI:10.3866/PKU.WHXB202301018
[Co3]簇基金属有机框架材料实现"一石二鸟"高效催化CO2转化为噁唑烷酮
[Co3]-Cluster Based Metal-Organic Framework Enables"Two Birds with One Stone"in Efficient Transformation of CO2 to Oxazolidinones
摘要
Abstract
CO2,as a greenhouse gas,has excessive emissions that lead to many environmental problems and is a rich and cheap C1 resource.Effective utilization and transformation of CO2 has become an important means of achieving carbon neutrality.Oxazolidinones are important intermediates in pharmaceutical chemistry that can be synthesized by carboxylation cyclization of CO2 with propargyl amines or cycloaddition of CO2 with aziridines.Owing to CO2's high stability,these reactions typically require harsh conditions,such as high temperatures or pressures.It is desirable,but challenging,to find a catalyst that can catalyze these two types of reactions under relatively mild conditions.Metal-organic frameworks(MOFs)are an emerging class of heterogeneous catalysts that with great potential in the catalytic conversion of CO2 to value-added products because of their attractive features,such as abundant metal active sites,inherent porosity,and easy functionalities.Herein,a unique three-dimensional(3D)MOF,{(CH3NH2CH3)2[Co3(BCP)2]·6H2O·4DMF}n(1)(H4BCP:5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid;DMF:N,N'-dimethylformamide),was synthesized using carboxylic acid ligands and cobalt salts via a solvothermal method.According to structural analysis,[Co3]clusters as secondary building units(SBU)are bridged by BCP4-ligands,forming an anion framework with flu topology,and dimethylamine cations act as counter ions in the pores.The framework has rectangular channels of approximately 0.4 nm×0.9 nm along the a-axis direction,exhibiting its porous property.Infrared spectroscopy(IR)and X-ray photoelectron spectroscopy(XPS)characterizations proved the coordination interaction between the carboxyl groups in the ligands and the metal ions.The powder X-Ray diffraction(PXRD)test further confirmed the phase purity of the synthesized samples.PXRD and thermogravimetry(TG)analyses indicated that 1 possessed good solvent and thermal stabilities.The catalytic experiments revealed that 1 could effectively catalyze CO2 with aziridines or propargyl amines to prepare oxazolidinones.In the cycloaddition of CO2 with aziridines,1 can facilitate the reaction under relatively mild conditions compared to other reported MOF-based catalysts.It shows excellent universality for substrates with various substitutions on the N atom or benzene ring.Investigation of the mechanism indicated that the coordination interaction of cobalt metal sites with the nitrogen atoms of aziridines can activate the substrates.For the carboxylative cyclization of CO2 with propargylic amines,this catalyst also has a broad substrate scope.Control experiments and nuclear magnetic resonance(NMR)tests suggest that Lewis acid metal sites are responsible for the high catalytic efficiency achieved by activating the alkyne groups.Moreover,1 showed good reusability in both reactions.Compound 1 represents a new catalyst that enables"two birds with one stone"in the catalytic synthesis of oxazolidinones using CO2.关键词
金属有机框架材料/双功能催化剂/CO2利用/噁唑烷酮/可循环性Key words
Metal-organic framework/Bifunctional catalyst/CO2 utilization/Oxazolidinone/Reusability分类
化学引用本文复制引用
焦卓浩,赵心远,赵健,谢瑶,侯胜利,赵斌..[Co3]簇基金属有机框架材料实现"一石二鸟"高效催化CO2转化为噁唑烷酮[J].物理化学学报,2023,39(11):95-102,8.基金项目
国家自然科学基金(92161202,22121005,21971125,22101138,21625103),中国博士后科学基金(2020T130319)与高等学校学科创新引智计划(B12015)资助项目 The project was supported by the National Natural Science Foundation of China(92161202,22121005,21971125,22101138,21625103),the China Postdoctoral Science Foundation(2020T130319),and the 111 Project,China(B12015). （92161202,22121005,21971125,22101138,21625103）
