Wang Qihaoyue, Lin Lin, Jiang Li, Wang Zihao, Zhang Yina, Han Qiance, Huang Xin, Zhu Changyan, Jia Jiangtao, Bian Zheng, Zhu Guangshan
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry, Northeast Normal University Changchun Jilin 130024 China
Chem Sci. 2025 Jul 1. doi: 10.1039/d5sc00355e.
Herein, we report the development of a post-synthetic modification approach to introduce a high loading of formyl groups onto porous aromatic framework (PAF)-5 Friedel-Crafts alkylation followed by hydrolysis. Rigorous characterization by NMR, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy authenticated the successful integration of aldehyde moieties into PAF-5, affording PAF-5-CHO. Subsequent functionalization of PAF-5-CHO with various amines produced three amine-functionalized PAF derivatives. Notably, PAF-5-C[double bond, length as m-dash]N-EDA exhibited a 78% enhancement in carbon dioxide (CO) adsorption capacity, reaching 3.78 mmol g at 1 bar and 298 K relative to PAF-5-CHO. Breakthrough experiments demonstrated that PAF-5-C[double bond, length as m-dash]N-EDA could effectively separate CO from simulated flue gas (CO/N = 15 : 85, v/v; 10 mL min). infrared spectroscopy, density functional theory calculations and temperature-programmed desorption studies provided insights into the CO adsorption mechanism.
在此，我们报道了一种后合成修饰方法的开发，该方法通过傅克烷基化反应随后水解，将高负载量的甲酰基引入到多孔芳香骨架（PAF）-5中。通过核磁共振（NMR）、X射线光电子能谱和傅里叶变换红外光谱进行的严格表征证实了醛基成功整合到PAF-5中，得到了PAF-5-CHO。随后用各种胺对PAF-5-CHO进行功能化，制备了三种胺功能化的PAF衍生物。值得注意的是，相对于PAF-5-CHO，PAF-5-C≡N-EDA在1巴和298K下的二氧化碳（CO₂）吸附容量提高了78%，达到3.78 mmol/g。突破实验表明，PAF-5-C≡N-EDA能够有效地从模拟烟道气（CO₂/N₂ = 15 : 85，v/v；10 mL/min）中分离出CO₂。红外光谱、密度泛函理论计算和程序升温脱附研究为CO₂吸附机理提供了深入见解。
