| Autor: |
Volante S; University of Pisa, Dipartimento di Chimica e Chimica Industriale, 56124 Pisa, Italy. giulio.bresciani@dcci.unipi.it.; CIRCC, Via Celso Ulpiani 27, I-70126 Bari, Italy., Kloda M; Institute of Inorganic Chemistry of the Czech Academy of Sciences, Husinec-Řež-1001, 250 68 Řež, Czech Republic., Demel J; Institute of Inorganic Chemistry of the Czech Academy of Sciences, Husinec-Řež-1001, 250 68 Řež, Czech Republic., Pampaloni G; University of Pisa, Dipartimento di Chimica e Chimica Industriale, 56124 Pisa, Italy. giulio.bresciani@dcci.unipi.it.; CIRCC, Via Celso Ulpiani 27, I-70126 Bari, Italy., Marchetti F; University of Pisa, Dipartimento di Chimica e Chimica Industriale, 56124 Pisa, Italy. giulio.bresciani@dcci.unipi.it.; CIRCC, Via Celso Ulpiani 27, I-70126 Bari, Italy., Bresciani G; University of Pisa, Dipartimento di Chimica e Chimica Industriale, 56124 Pisa, Italy. giulio.bresciani@dcci.unipi.it.; CIRCC, Via Celso Ulpiani 27, I-70126 Bari, Italy., Taddei M; University of Pisa, Dipartimento di Chimica e Chimica Industriale, 56124 Pisa, Italy. giulio.bresciani@dcci.unipi.it.; CIRCC, Via Celso Ulpiani 27, I-70126 Bari, Italy. |
| Abstrakt: |
In the synthesis of metal-organic frameworks (MOFs), the choice of the metal precursor plays a key role because of the influence that it can exert on the crystallization kinetics. The present work explores the use of metal-carbamato complexes for the synthesis of benchmark MOFs, namely HKUST-1 and UiO-66. Cu 2 (O 2 CNEt 2 ) 4 ·2NHEt 2 and Zr(O 2 CNEt 2 ) 4 , prepared using straightforward CO 2 fixation reactions starting from the corresponding metal chlorides and diethylamine, were employed as metal precursors for MOF formation. The synthesis conditions, including the solvent, temperature, and ligand protonation degree, were systematically investigated, revealing metal carbamates as highly reactive precursors due to their prompt release of CO 2 and amine upon reaction with protic species, i.e. , the polycarboxylic linkers. This property of metal carbamates allowed us to identify room temperature protocols to achieve MOFs with comparable properties to those obtained using traditional metal precursors. Subsequent optimization of the reaction conditions led to the design of a one-pot synthetic strategy for HKUST-1, starting directly from copper(II) chloride and diethylamine under a CO 2 atmosphere. The MOFs were characterized using various techniques, including powder X-ray diffraction, N 2 sorption analysis, 1 H nuclear magnetic resonance spectroscopy, and CHN elemental analysis, and compared to reference samples prepared according to literature procedures. |
