Department of Chemistry, University of Science and Technology of China, Hefei 230026, PR China.
J Phys Chem B. 2010 Mar 11;114(9):3404-10. doi: 10.1021/jp100308x.
A novel molecule-ion adduct of ammonium molybdate tetrahydrate (AMT) with beta-cyclodextrin (CD) was prepared in this work. Significant differences in spectral properties between AMT and the adduct AMT-beta-CD were observed by a series of experimental probes, such as powder X-ray diffraction, Fourier transformation infrared spectroscopy, and Raman spectroscopy. Field emission scanning electron microscopy showed that, although the crystal growth of AMT-beta-CD was dominated by the molecular stacking of AMT, the size and morphology of the adduct were rather different from those seen in free AMT. The difference in stacking forms was attributed to the contribution of the molecule-ion interaction between AMT and beta-CD. A drastic improvement in thermal stability of AMT and beta-CD after adduct formation was observed by thermogravimetry analysis, which was confirmed by controlled sintering measurements. This revealed that the adduct interaction between them played an important role in mediating the thermal decomposition process of the adducted components. Furthermore, our results indicated that AMT and its adduct had a different performance in the catalytic desulfurization of thiophene and its derivatives. The fact that the catalytic efficiency of AMT was decreased after adduct formation implied there was a complexation between AMT and beta-CD. Besides, several unusual molecular ions--NH(3)(+), NH(2)(+), and NH(+)--were simultaneously found with gas chromatography coupled to time-of-flight mass spectrometry of free AMT.
本文制备了钼酸铵四水合物(AMT)与β-环糊精(CD)的新型分子-离子加合物。通过一系列实验探针,如粉末 X 射线衍射、傅里叶变换红外光谱和拉曼光谱,观察到 AMT 和加合物 AMT-β-CD 在光谱性质上存在显著差异。场发射扫描电子显微镜表明,尽管 AMT-β-CD 的晶体生长主要由 AMT 的分子堆积主导,但加合物的大小和形态与游离 AMT 明显不同。堆积形式的差异归因于 AMT 和 CD 之间的分子-离子相互作用的贡献。热重分析观察到 AMT 和 CD 形成加合物后热稳定性有明显提高,这一结果通过控制烧结测量得到了证实。这表明它们之间的加合物相互作用在调节加合物成分的热分解过程中起着重要作用。此外,我们的结果表明 AMT 及其加合物在噻吩及其衍生物的催化脱硫中表现出不同的性能。AMT 形成加合物后催化效率降低的事实表明 AMT 与 CD 之间存在络合作用。此外,在游离 AMT 的气相色谱-飞行时间质谱分析中,还同时发现了几种异常的分子离子--NH(3)(+)、NH(2)(+)和 NH(+)。