文献类型：期刊文献

英文题名：Room-Temperature Single-Phase Synthesis of Semiconducting Metal-Covalent Organic Frameworks With Microenvironment-Tuned Photocatalytic Efficiency

作者：Wu, Dongchuang[1,2];Zhang, Qiongshan[1];Yin, Shiyu[1];Song, Congying[3];Gu, Ning[2];Wang, Dong[1];Cai, Tao[3];Zhang, Bin[1,4]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]North Univ China, Sch Energy & Power Engn, Taiyuan 030051, Peoples R China;[3]Wuhan Univ, Coll Chem & Mol Sci, State Key Lab Power Grid Environm Protect, Wuhan 430072, Hubei, Peoples R China;[4]East China Univ Sci & Technol, Shanghai Key Lab Intelligent Sensing & Detect, Shanghai 200237, Peoples R China

年份：2025

卷号：9

期号：4

外文期刊名：SMALL METHODS

收录：;EI(收录号：20244117183682);WOS:【SCI-EXPANDED(收录号:WOS:001330031500001)】；

基金：D W, Q Z and S Y is contributed equally to this work. The authors acknowledge the financial support from the Innovative Research Group Project of the National Natural Science Foundation of China (52321002), the National Key Research and Development Program of China (2021YFB3501900), National Natural Science Foundation of China (52473171, 22273021), Shanxi Provincial Natural Science Foundation (202403021212051), Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (2024L166), the National Science Foundation of Shanghai (23ZR1416900), and the Fundamental Research Funds Administered by Wuhan University (600460001).

语种：英文

外文关键词：crystallinity mechanism; dynamic growth; metal-covalent organic frameworks; planarity-tuned growth; single-phase synthesis

摘要：In order to improve the solubility of metallated monomers and product crystallinity, metal-covalent organic frameworks (MCOFs) are commonly prepared via high-temperature sol-vothermal synthesis. However, it hampers the direct extraction of crystallization evolution information. Exploring facile room-temperature strategies for both synthesizing MCOFs and exploiting the crystallinity mechanism is extremely desired. Herein, by a novel single-phase synthetic strategy, three MCOFs with different microstructure is rapidly prepared based on the Schiff base reaction between planarity-tunable C3v monomers and metallated monomers at room temperature. Based on detailed time-dependent experiments and theoretical calculations, it is found that there is a planarity-tuned and competitive growth relationship between disordered structures and crystal nucleus for the first time. The high planarity of monomers boosts the formation of crystal nucleus and rapid growth, suppressing the forming of amorphous structures. In addition, the microenvironment effect on selective photocatalytic coupling of benzylamine (BA) is investigated. The strong donor-acceptor (D-A) MCOF exhibits efficient photocatalytic activity with a high conversion rate of 99% and high selectivity of 99% in 5 h under the 520 nm light irradiation. This work opens a new pathway to scalable and efficient synthesis of highly crystalline MCOFs. A room-temperature single-phase synthetic strategy for rapidly preparing planarity is reported and microenvironment-tunable semiconducting MCOFs based on the Schiff base reaction between C3v monomers with different geometric configurations and metalated monomers. It can be observed that there is a planarity-tuned and competitive growth relationship between disordered structures and crystal nucleus for the first time. image