Wu Jinyi, Ma Shasha, Cui Jiawei, Yang Zujin, Zhang Jianyong
MOE Laboratory of Polymeric Composite and Functional Materials, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, China.
School of Chemical Engineering and Technology, Sun Yat-sen University, Guangzhou 510275, China.
Nanomaterials (Basel). 2022 Sep 6;12(18):3088. doi: 10.3390/nano12183088.
As CO emissions increase and the global climate deteriorates, converting CO into valuable chemicals has become a topic of wide concern. The development of multifunctional catalysts for efficient CO conversion remains a major challenge. Herein, two porous organic polymers (NPOPs) functionalized with covalent triazine and triazole -heterocycles are synthesized through the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. The NPOPs have an abundant microporous content and high specific surface area, which confer them excellent CO affinities with a CO adsorption capacity of 84.0 mg g and 63.7 mg g, respectively, at 273 K and 0.1 MPa. After wet impregnation and in situ reductions, Ag nanoparticles were supported in the NPOPs to obtain Ag@NPOPs with high dispersion and small particle size. The Ag@NPOPs were applied to high-value conversion reactions of CO with propargylic amines and terminal alkynes under mild reaction conditions. The carboxylative cyclization transformation of propargylic amine into 2-oxazolidinone and the carboxylation transformation of terminal alkynes into phenylpropiolic acid had the highest TOF values of 1125.1 and 90.9 h, respectively. The Ag@NPOP-1 was recycled and used five times without any significant decrease in catalytic activity, showing excellent catalytic stability and durability.
随着一氧化碳排放量的增加和全球气候的恶化,将一氧化碳转化为有价值的化学品已成为一个广受关注的话题。开发用于高效一氧化碳转化的多功能催化剂仍然是一项重大挑战。在此,通过铜(I)催化的叠氮化物-炔烃环加成(CuAAC)反应合成了两种用共价三嗪和三唑杂环官能化的多孔有机聚合物(NPOPs)。NPOPs具有丰富的微孔含量和高比表面积,这赋予它们优异的一氧化碳亲和力,在273K和0.1MPa下,一氧化碳吸附容量分别为84.0mg/g和63.7mg/g。经过湿浸渍和原位还原后,将银纳米颗粒负载在NPOPs中,得到具有高分散性和小粒径的Ag@NPOPs。将Ag@NPOPs应用于在温和反应条件下一氧化碳与炔丙胺和末端炔烃的高价值转化反应。炔丙胺羧基环化转化为2-恶唑烷酮以及末端炔烃羧化转化为苯丙炔酸的最高TOF值分别为1125.1和90.9h-1。Ag@NPOP-1循环使用五次,催化活性没有任何显著下降,显示出优异的催化稳定性和耐久性。