Department of Chemistry, Kyungpook National University, Daegu 702-701, Korea.
Phys Chem Chem Phys. 2010 Mar 20;12(11):2625-31. doi: 10.1039/b921558a. Epub 2010 Jan 6.
A typical MOF material, Cu-BTC has been synthesized with microwave and conventional electric heating in various conditions to elucidate, for the first time, the quantitative acceleration in the synthesis of a MOF by microwaves. The acceleration by microwaves is mainly due to rapid nucleation rather than rapid crystal growth, even though both stages are accelerated. The acceleration in the nucleation stage by microwaves is due to the very large pre-exponential factor (about 1.4 x 10(10) times that of conventional synthesis) in the Arrhenius plot. However, the activation energy for the nucleation in the case of microwave synthesis is higher than the activation energy of conventional synthesis. The large acceleration in the nucleation, compared with that in the crystal growth, is observed once again by the syntheses in two-steps (changing heating methods from microwave into conventional heating or from conventional heating into microwave heating just after the nucleation is completed). The crystal size of Cu-BTC obtained by microwave-nucleation is generally smaller than the Cu-BTC made by conventional-nucleation, probably due to rapid nucleation and the small size of nuclei with microwave-nucleation.
一种典型的 MOF 材料,Cu-BTC,已经通过微波和常规电加热在不同条件下被合成,首次阐明了微波对 MOF 合成的定量加速作用。微波的加速作用主要是由于快速成核而不是快速晶体生长,尽管这两个阶段都被加速了。微波对成核阶段的加速是由于在阿累尼乌斯图中的非常大的前置指数因子(大约是常规合成的 1.4 x 10(10)倍)。然而,在微波合成的情况下,成核的活化能高于常规合成的活化能。一旦在两步法合成(在成核完成后将加热方法从微波转换为常规加热或从常规加热转换为微波加热)中再次观察到成核的加速比晶体生长的加速大得多。通过微波成核获得的 Cu-BTC 的晶体尺寸通常小于通过常规成核获得的 Cu-BTC,这可能是由于微波成核的快速成核和小核的尺寸。