Synthesis and alcohol catalytic properties of TEMPO functionalized Zr-based MOFs

• Published in: Cai liao gong cheng = Journal of materials engineering Vol. 48; no. 10; pp. 169 - 175
• Main Authors: Zhuang, Jin-Liang, Liu, Xiang-Yue, Du, Xuan
• Format: Journal Article
• Language: Chinese
• Published: Beijing Beijing Institute of Aeronautical Materials 01-10-2020; Journal of Materials Engineering
• Subjects: Acetic acid; Alcohol; alcohol oxida-tion; Benzaldehyde; Benzyl alcohol; Catalysis; Catalytic activity; Chemical synthesis; Dicarboxylic acids; Dyes; Nanocrystals; Nitrogen dioxide; organocatalyst; Oxidation; porous material; radical; Selectivity; Zirconium; zr-based metal-organic framework
• ISSN: 1001-4381; 1001-4381
• DOI: 10.11868/j.issn.1001-4381.2020.000455

A strategy based on grafting organocatalytic units as side-chain on the organic linkers, a TEMPO radical decorated terphenyl-dicarboxylic acid linker was synthesized. By employing acetic acid as modulator, TEMPO radical decorated UiO-68-TEMPO nanocrystals were synthesized by using H2tpdc-TEMPO as organic linker and ZrOCl2 as metal source under solvothermal conditions. UiO-68-TEMPO are monodispersed nanocrystals with side in the range of 800-1200 nm, with high BET areas (up to 1320 m2/g), and contain a large number of TEMPO radicals as evidenced by solid-state EPR spectrum. UiO-68-TEMPO nanocrystals enable selective oxidation of a broad range of alcohols, including primary aromatic alcohols, secondary aromatic alcohols, and heterogeneous atomic alcohols, with high efficiency and selectivity. The catalytic activity of UiO-68-TEMPO nanocrystals remains 75% after catalysis for four cycles. Finally, a plausible catalytic mechanism for the oxidation of benzyl alcohol by UiO-68-TEMPO was proposed, that is the TBN co