Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Adv Mater. 2019 Dec;31(50):e1904976. doi: 10.1002/adma.201904976. Epub 2019 Nov 7.
Novel porous polymers can serve as self-supporting solid carriers and provide abundant coordination or charged sites for single-site metals, and thus are emerging as advanced functional materials in heterogeneous catalysis for various transformations traditionally catalyzed by homogeneous systems. A brief overview of the development of this heterogenization given, including the recent advances regarding electrovalent bonds by employing charged supports represented by porous ionic polymers (PIPs), which is exemplified herein with a novel single-site Rh /PIP catalyst, featuring a new active site [Rh(CO)I ] dual-ionically bound onto a quaternary phosphonium cationic framework polymer, different from the single-ionically bound [Rh(CO) I ] in previous studies. Such a unique metal configuration of Rh /PIP leads to excellent performance in vapor-phase methanol carbonylation, outperforming commercial homo- and heterogeneous catalysts.
新型多孔聚合物可用作自支撑固体载体，为单原子金属提供丰富的配位或带电位，因此作为新型功能材料在多相催化中异军突起，在各种转化中取代传统的均相体系。本文简要综述了这一异相化的发展，包括利用多孔离子聚合物(PIPs)等带电载体形成的电共价键的最新进展，新型 Rh/PIP 单原子催化剂即为一例，其具有新型活性位[Rh(CO)I]，通过与季膦阳离子骨架聚合物的双离子键合，与以往研究中的单离子键合[Rh(CO)I]不同。这种 Rh/PIP 的独特金属构型导致其在甲醇气相羰基化反应中表现出优异的性能，优于商业均相和多相催化剂。
