中科院宁波材料所张涛团队报道了单层辅助表面引发席夫碱介导的醛醇缩聚合成结晶sp²C共轭共价有机框架薄膜。相关研究成果发表在2023年2月13日出版的《美国化学会杂志》。

sp²碳共轭共价有机框架（sp²C COFs）具有优异的面内π共轭、高化学稳定性和坚固的框架结构，有望成为广泛应用的理想膜/膜，包括能源相关器件和光电子。然而，到目前为止，sp²C COFs主要局限于微晶粉末，因此阻碍了它们在器件中的性能。

该文中，研究人员报告了一种简单而稳健的方法，通过自组装单层辅助表面引发的席夫碱介导的醛醇缩聚（即SI-SBMAP），在各种固体基底（例如，氟掺杂的氧化锡、铝板、聚丙烯腈膜）上制备大面积、独立和结晶的sp²C COF膜（TFPT–TMT和TB–TMT）。所得sp²C COFs膜显示出高达120cm²的横向尺寸和从几十纳米到几微米的可调厚度。由于坚固的框架和高度有序的准一维通道，基于sp²C COF膜的渗透功率发生器在恶劣条件下的输出功率密度为14.1 W m^–2，优于大多数报道的COF膜以及商业化的基准装置（5 W m^–1）。

该项工作展示了一种用于绿色能源应用和潜在光电子的sp²C COF膜/膜的简单而稳健的界面方法。

附：英文原文

Title: Monolayer-Assisted Surface-Initiated Schiff-Base-Mediated Aldol Polycondensation for the Synthesis of Crystalline sp2 Carbon-Conjugated Covalent Organic Framework Thin Films

Author: Ke Wang, Haoyong Yang, Zhongquan Liao, Shengxu Li, Mike Hambsch, Guangen Fu, Stefan C. B. Mannsfeld, Qi Sun, Tao Zhang

Issue&Volume: February 13, 2023

Abstract: sp2 carbon-conjugated covalent organic frameworks (sp2c-COFs) with superb in-plane π-conjugations, high chemical stability, and robust framework structure are expected to be ideal films/membranes for a wide range of applications including energy-related devices and optoelectronics. However, so far, sp2c-COFs have been mainly limited to microcrystalline powders, and this consequently hampered their performances in devices. Herein, we report a simple and robust methodology to fabricate large-area, free-standing, and crystalline sp2c-COF films (TFPT–TMT and TB–TMT) on various solid substrates (e.g., fluorine-doped tin oxide, aluminum sheet, polyacrylonitrile membrane) by self-assembly monolayer-assisted surface-initiated Schiff-base-mediated aldol polycondensation (namely, SI-SBMAP). The resultant sp2c-COF films show lateral sizes up to 120 cm2 and tunable thickness from tens of nanometers to a few micrometers. Owing to the robust framework and highly ordered quasi-1D channels, the sp2c-COF membrane-based osmotic power generator presents an output power density of 14.1 W m–2 under harsh conditions, outperforming most reported COF membranes as well as commercialized benchmark devices (5 W m–2). This work demonstrates a simple and robust interfacial methodology for the fabrication of sp2c-COF films/membranes for green energy applications and potential optoelectronics.

DOI: 10.1021/jacs.2c12186

Source: https://pubs.acs.org/doi/10.1021/jacs.2c12186