Covalent-Bonding Oxidation Group and Titanium Cluster to Synthesize a Porous Crystalline Catalyst for Selective Photo-Oxidation Biomass Valorization

被引：90
作者：
Chang, Jia-Nan [1 ]
Li, Qi [1 ]
Yan, Y. [2 ]
Shi, Jing-Wen [1 ]
Zhou, Jie [2 ]
Lu, Meng [2 ]
Zhang, Mi [2 ]
Ding, Hui-Min [1 ]
Chen, Yifa [2 ]
Li, Shun-Li [2 ]
Lan, Ya-Qian [2 ]
机构：
[1] Nanjing Normal Univ, Sch Chem & Mat Sci, Jiangsu Key Lab New Power Batteries, Jiangsu Collaborat Innovat Ctr Biomed Funct Mat, Nanjing 210023, Peoples R China
[2] South China Normal Univ, Sch Chem, Guangzhou 510006, Peoples R China
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2022年 / 61卷 / 37期
关键词：
2; 5-Furandicarboxylic Acid; 5-Hydroxymethylfurfural; Biomass; Covalent Organic Framework; Photocatalysis; 2,5-FURANDICARBOXYLIC ACID; ORGANIC FRAMEWORK; METAL; PHOTOCATALYST; MECHANISM; DESIGN;
D O I：
10.1002/anie.202209289
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The selective photo-oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is important due to its substitute-role in polyester-fabrication. Here, a titanium-cluster based metal-covalent organic framework nanosheet has been synthesized through the covalent-coupling between Ti-6-NH2 and benzotrithiophene tricarbaldehyde (BTT). The integration of them endows the nanosheet with a visible-light-adsorption region, effective electron-hole separation-efficiency and suitable photo-oxidation ability. Specifically, its photo-selectivity for HMF-to-FDCA can be >95 % with approximate to 100 % conversion, which is more than 2, 5, and 10 times higher than MOF-901 (43 %), Ti-6-NH2 (19 %) and under-darkness (9 %), respectively. Notably, an O-2-based mechanism is proposed and the vital roles of Ti-6-NH2 and BTT are verified by DFT calculations. This work might facilitate the exploration of porous-crystalline-catalysts for selective biomass-valorization.
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页数：8
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