Zhang Hao, Li Cha, Lang Feifan, Li Mei, Liu Haoyu, Zhong Di-Chang, Qin Jun-Sheng, Di Zhengyi, Wang Dan-Hong, Zeng Le, Pang Jiandong, Bu Xian-He
School of Materials Science and Engineering, Smart Sensing Interdisciplinary Science Center, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin, 300350, P. R. China.
Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384, P. R. China.
Angew Chem Int Ed Engl. 2025 Feb 3;64(6):e202418017. doi: 10.1002/anie.202418017. Epub 2024 Dec 11.
Precise adjusting the band gaps in metal-organic frameworks (MOFs) is crucial for improving their visible-light absorption capacity during photocatalysis, presenting both a formidable challenge and a charming opportunity. This present study employed a symmetry-reduction strategy to pre-design six novel 4-connected ligands with systematic substituents (-NO, -H, -Bu, -OCH, -OH and -NH) and synthesized the corresponding pillared-layer Zr-MOFs (NKM-668) retaining the hexaphenylbenzene fragment. Subsequently, the NKM-668 MOFs were transformed into large-π-conjugated hexabenzocoronene-based MOFs (pNKM-668) via the Scholl reaction. These twelve MOFs exhibited broad and tunable band gaps over 1.41 eV (ranging from 3.25 eV to 1.84 eV), and the photocatalytic CO conversion rate raised by 33.2-fold. This study not only enriches the type of hexaphenylbenzene-based MOFs, but also paves the way for nanographene-containing MOFs in the further application of photocatalysis.
精确调节金属有机框架材料（MOFs）的带隙对于提高其在光催化过程中的可见光吸收能力至关重要，这既带来了巨大挑战，也提供了诱人机遇。本研究采用对称性降低策略预先设计了六种带有系统取代基（-NO、-H、-Bu、-OCH、-OH和-NH）的新型四连接配体，并合成了保留六苯基苯片段的相应柱状层Zr-MOFs（NKM-668）。随后，通过肖尔反应将NKM-668 MOFs转化为基于大π共轭六苯并蔻的MOFs（pNKM-668）。这十二种MOFs表现出超过1.41 eV的宽且可调的带隙（范围从3.25 eV到1.84 eV），并且光催化CO转化率提高了33.2倍。本研究不仅丰富了基于六苯基苯的MOFs的类型，也为含纳米石墨烯的MOFs在光催化的进一步应用铺平了道路。
