Ram Kishan, Pooja Rani, Gulshan Singh, C. M. Nagaraja
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引用次数: 0
摘要
捕获和利用二氧化碳以可持续方式合成商品产品,是缓解大气中二氧化碳含量不断增加以改善环境的重要举措。同时,Suzuki-Miyaura 和 Mizoroki-Heck 交叉偶联反应是生成有价值的原料化合物(如农用化学品、天然产品和药物等)的重要工具。在这方面,我们介绍了通过后合成修饰将催化活性钯(II)战略性地加入由双吡啶位点组成的多孔共价三嗪框架(CTF)(mby-CTF)的方法。值得注意的是,锚定钯(II)框架 Pd(II)@bpy-CTF 在 CO2 与丙炔胺的环化反应和交叉偶联反应(Heck 和 Suzuki-Miyaura)中表现出卓越的催化功能,在温和的条件下生成高价值的商品。此外,以 Pd(II)@bpy-CTF 为催化剂,还能将各种电子和立体上具有挑战性的底物转化为相应的产物。值得注意的是,Pd(II)@bpy-CTF 表现出高效的可重复使用性,可维持八个催化循环而不会发生实质性降解。Pd(II)@bpy-CTF 的卓越催化性能归功于 CTF 一维通道中大量富含 N 的三嗪单元和暴露的催化 Pd(II) 位点。这项工作证实了基于三嗪的框架在利用二氧化碳和稳定催化活性金属离子方面的潜在用途,可用于开发高度可回收的催化剂,从而高效地生产出高附加值的化学品。
Functionalized Covalent Triazine Framework (CTF) for Catalytic CO2 Fixation and Synthesis of Value-Added Chemicals
The capture and utilization of CO2 for sustainable synthesis of commodity products represent a significant move toward mitigating the growing atmospheric CO2 content for environmental remediation. Meanwhile, Suzuki-Miyaura and Mizoroki-Heck cross-coupling reactions are considerable tools for generating valuable feedstock compounds, such as agrochemicals, natural products, drugs, etc. In this regard, we present the strategic incorporation of catalytically active Pd(II) in a porous covalent triazine framework (CTF) composed of bipyridine sites (bpy-CTF) by postsynthetic modification. Notably, Pd(II) anchored framework, Pd(II)@bpy-CTF, demonstrated exceptional catalytic function in the cyclization of CO2 with propargylic amines and in cross-coupling reactions (Heck and Suzuki-Miyaura), producing high-value commodity products under mild conditions. Further, various electronically and sterically challenging substrates were converted into the corresponding products by using Pd(II)@bpy-CTF as a catalyst. Notably, Pd(II)@bpy-CTF exhibited efficient reusability, sustaining eight catalytic cycles without substantial degradation. The exceptional catalytic behavior of Pd(II)@bpy-CTF is accredited to high abundance of N-rich triazine units and the exposed catalytic Pd(II) sites within the one-dimensional channels of the CTF. This work establishes the potential utility of triazine-based frameworks for utilizing carbon dioxide and stabilizing catalytically active metal ions in developing highly recyclable catalysts to generate value-added chemicals efficiently.
期刊介绍:
The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials.
Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.