近日，中国科学院化学研究所万立骏团队实现了酯-胺交换反应直接合成酰胺连接的COFs。该研究于2025年8月18日发表在《美国化学会志》上。

对于共价有机框架（COFs）而言，同时实现结晶度和稳定性是一项挑战，因为提高结晶度所需的可逆反应会损害稳定性。酰胺键是COF结构中一种化学稳定的键，主要通过后修饰合成。

研究组提出了一种通过酯胺交换反应合成高结晶性酰胺连接COFs的简便方法。对模型反应和COFTAPT-TTPF聚合过程的研究表明，该反应是不可逆的。在25℃、94%相对湿度条件下，COFTAPT-TTPF的吸水量为0.56 g/g。同时，通过直接合成，研究组在阳极氧化铝膜上生长了COFTAPT-TTPF，形成COF@AAO复合膜。在50倍盐度梯度下，复合膜的渗透能转换输出功率密度达到7.70 W/m²。这种直接聚合方案提高了酰胺连接COFs的便利性和可及性。

附：英文原文

Title: Direct Synthesis of Amide-Linked COFs via Ester-Amine Exchange Reaction

Author: Rui-Zhi Li, Song-Chen Yu, Wei Jiang, Jiale Zhou, Zi-Cong Wang, Xiao-Rui Ren, Wei Feng, Yahong Zhou, Dong Wang, Li-Jun Wan

Issue&Volume: August 18, 2025

Abstract: Achieving both crystallinity and stability is challenging for covalent organic frameworks (COFs) as the reversible reaction required for enhancing crystallinity compromises stability. Amide linkages, a type of chemically stable bond for COF construction, are predominantly synthesized via postmodifications. This work presents a direct and convenient method for synthesizing highly crystalline amide-linked COFs via the ester-amine exchange reaction. The reaction is irreversible, as demonstrated by the investigation of model reactions and COFTAPT-TTPF polymerization process. The water absorption capacity of COFTAPT-TTPF was 0.56 g/g at 25 °C and 94% relative humidity. Meanwhile, via direct synthesis, we grew COFTAPT-TTPF on anodized aluminum oxide membranes to form COF@AAO composite membranes. The composite membrane achieved an output power density of 7.70 W/m2 under a 50-fold salinity gradient in osmotic energy conversion. This direct polymerization protocol improves the convenience and accessibility of amide-linked COFs.

DOI: 10.1021/jacs.5c08823

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c08823