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

Authors :: Chang JN
Li Q
Yan Y
Shi JW
Zhou J
Lu M
Zhang M
Ding HM
Chen Y
Li SL
Lan YQ
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Sep 12; Vol. 61 (37), pp. e202209289. Date of Electronic Publication: 2022 Aug 03.
Publication Year :: 2022
Abstract: 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 <subscript>6</subscript> -NH <subscript>2</subscript> 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 ≈100 % conversion, which is more than 2, 5, and 10 times higher than MOF-901 (43 %), Ti <subscript>6</subscript> -NH <subscript>2</subscript> (19 %) and under-darkness (9 %), respectively. Notably, an O <subscript>2</subscript> -based mechanism is proposed and the vital roles of Ti <subscript>6</subscript> -NH <subscript>2</subscript> and BTT are verified by DFT calculations. This work might facilitate the exploration of porous-crystalline-catalysts for selective biomass-valorization.<br /> (© 2022 Wiley-VCH GmbH.)

Subjects :: Biomass
Furaldehyde chemistry
Furans chemistry
Porosity
Dicarboxylic Acids chemistry
Titanium chemistry

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