固体推进剂中的维生素:中性大分子键合剂的可控合成
王振, 冯浩洋, 邵晓阳, 范文如
【大学化学】doi: 10.3866/PKU.DXHX202401007
复合固体推进剂是一种固体颗粒(氧化剂及金属燃料)填充高分子聚合物(粘合剂)的复合材料,是导弹、空间飞行器的各类固体发动机的动力源。本实验教学针对固体推进剂在载荷下容易发生“脱湿”,即粘合剂与填料表面之间分离,界面作用受到破坏的情况,通过可控自由基聚合设计了结构规整、分子量及组成可控的新型中性大分子键合剂,通过核磁氢谱及凝胶渗透色谱系统表征了其分子结构。本综合实验教学不仅加深了学生对固体推进剂领域的理解,提升了学生对于前沿高分子化学的基本原理及方法的认知,而且训练了学生的实验操作技能、大型仪器使用能力和结果分析能力,实现了前沿科学研究与国家重大需求在人才培养的结合。
关键词: 固体推进剂, 大分子键合剂, 可控自由基聚合, 界面作用
Hydrogenation of CO2 to formate catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated iridium(Ⅰ) complexes
Huihua GONG, Tianhua CUI, Li JI, Jichuan ZHANG, Liyuan ZHANG, Yan CHEN, Zhenye WANG, Jiaqi XU, Ruixiang LI
【无机化学学报】doi: 10.11862/CJIC.20250170
To achieve efficient catalytic hydrogenation of CO₂ to formate, we employed a transmetallation strategy to develop three novel iridium(Ⅰ) complexes, which feature N-heterocyclic carbene-nitrogen-phosphine ligands (CNP) and a 1, 5-cyclooctadiene (cod) molecule: [Ir(cod)(κ3-CNimP)]Cl (1-Cl), [Ir(cod)(κ3-CNimP)]PF6 (1-PF6), and [Ir(cod)(κ3-CNHP)]Cl (2). The 1H NMR spectra, 31P NMR spectra, and high-resolution mass spectra verify the successful synthesis of these three Ir(Ⅰ)-CNP complexes. Furthermore, single-crystal X-ray diffraction analysis confirms the coordination geometry of 1-PF6. The strong Ir—C(NHC) bond suggests that the carbene carbon plays an enhanced anchoring role to iridium due to its strong σ-donating ability, which helps stabilize the active metal species during CO2 hydrogenation. As a result, the Ir(Ⅰ)-CNP complex exhibits remarkable activity and long catalytic lifetime for the hydrogenation of CO2 to formate, reaching a turnover number (TON) of 1.16×106 after 150 h at a high temperature of 170 ℃, which was a relatively high value among all the Ir complexes.
关键词: CO2 hydrogenation, iridium complex, CNP ligands, homogeneous catalysis

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