Chen Mingzhe, Wu Qiumin, Lin Chuncheng, Zhang Jiarui, Zhao Jigang, Chen Jinzhu, Xu Yisheng
State Key Laboratory of Chemical Engineering, International Joint Research Center of Green Energy Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China.
Department of Chemistry, College of Chemistry and Materials Science, Jinan University, No. 855, East Xingye Avenue, Panyu District, Guangzhou 511443, China.
ACS Appl Mater Interfaces. 2020 Sep 9;12(36):40236-40247. doi: 10.1021/acsami.0c08001. Epub 2020 Aug 26.
Chemical transformation of carbon dioxide (CO) into fine chemicals such as oxazolidinones and carbamates is mainly reported using transition-metal complexes as homogeneous catalysts. Herein, we demonstrate that a heterogeneous catalyst of highly dispersed Cu (Cu/NHPC) supported on hierarchically porous N-doped carbon (NHPC) can efficiently promote CO fixations to oxazolidinones and β-oxopropylcarbamates. The obtained NHPC, assembled by ultrathin nitrogen-doped carbon nanosheets with a three-dimensional (3D) structure, is readily prepared by pyrolysis of a nitrogen-containing polymer gel (NPG) in the presence of an activator of potassium bicarbonate (KHCO). The resulting NHPC shows specific Brunauer-Emmet-Teller (BET) surface areas up to 2054 m g with a mean micro/mesopore size of 0.55/3.2 nm and a broad macropore size distribution from 50 to 230 nm. The Cu/NHPC can efficiently promote three-component coupling of CO, amines, and propargyl alcohols for syntheses of various oxazolidinones and β-oxopropylcarbamates with yields up to 99% and a wide substrate scope. Moreover, the Cu/NHPC exhibits excellent recyclability in CO-to-oxazolidinone transformation during nine-time recycling. The research thus develops an NHPC-based heterogeneous Cu catalyst for green transformation of CO.
二氧化碳（CO₂）向恶唑烷酮和氨基甲酸酯等精细化学品的化学转化主要报道是使用过渡金属配合物作为均相催化剂。在此，我们证明了负载在分级多孔氮掺杂碳（NHPC）上的高度分散的铜（Cu/NHPC）非均相催化剂能够有效地促进CO₂固定生成恶唑烷酮和β-氧代丙基氨基甲酸酯。所制备的NHPC由具有三维（3D）结构的超薄氮掺杂碳纳米片组装而成，通过在碳酸氢钾（KHCO₃）活化剂存在下对含氮聚合物凝胶（NPG）进行热解即可轻松制备。所得的NHPC表现出高达2054 m²/g的比布鲁诺尔-埃米特-泰勒（BET）表面积，平均微孔/介孔尺寸为0.55/3.2 nm，大孔尺寸分布范围为50至230 nm。Cu/NHPC能够有效地促进CO₂、胺和炔丙醇的三组分偶联反应，用于合成各种恶唑烷酮和β-氧代丙基氨基甲酸酯，产率高达99%，底物范围广泛。此外，Cu/NHPC在九次循环的CO₂转化为恶唑烷酮的过程中表现出优异的可回收性。因此，该研究开发了一种用于CO₂绿色转化的基于NHPC的非均相铜催化剂。
