Sprung Christoph, Weckhuysen Bert M
Inorganic Chemistry and Catalysis, Department of Chemistry, Faculty of Science, Utrecht University , Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
J Am Chem Soc. 2015 Feb 11;137(5):1916-28. doi: 10.1021/ja511381f. Epub 2015 Jan 30.
A detailed and systematic polarized confocal fluorescence microscopy investigation is presented on three batches of large coffin-shaped ZSM-5 crystals (i.e., parent, steamed at 500 °C, and steamed at 700 °C). In total, six laser lines of different wavelength in the visible region are employed on two crystal positions and three orientations with respect to the polarization plane of the excitation laser light. A fluorescent probe molecule is generated inside the zeolite pores, originating from the acid-catalyzed oligomerization of 4-fluorostyrene. A thorough analysis of the polarization plane of emitting fluorescent light reveals insight into the orientation of the fluorescent probe molecule restricted by the highly ordered zeolite channel framework, thereby visualizing pore accessibility and clearly distinguishing the occupation of straight and sinusoidal channels by the probe molecule. Spectral features are, furthermore, observed to tell apart molecules situated in one or the other pore. Special focus was given on the rim and tip regions of the zeolite ZSM-5 crystals. On the basis of the confocal approach of the investigation, the aforementioned features are evaluated in three dimensions, while the degradation of the zeolite framework upon postsynthesis steam treatment could be visualized by occupation of the sinusoidal pores.
本文对三批大型棺材状ZSM-5晶体(即母体、在500℃下蒸汽处理以及在700℃下蒸汽处理的晶体)进行了详细而系统的偏振共聚焦荧光显微镜研究。总共在可见区域使用了六条不同波长的激光线,分别作用于晶体的两个位置以及相对于激发激光偏振平面的三个取向。荧光探针分子在沸石孔内产生,源于4-氟苯乙烯的酸催化低聚反应。对发射荧光的偏振平面进行的深入分析揭示了受高度有序的沸石通道框架限制的荧光探针分子的取向,从而直观地显示了孔的可及性,并清楚地区分了探针分子对直通道和正弦通道的占据情况。此外,还观察到光谱特征以区分位于不同孔中的分子。特别关注了ZSM-5沸石晶体的边缘和尖端区域。基于该研究的共聚焦方法,上述特征在三维空间中进行了评估,而后合成蒸汽处理后沸石框架的降解情况可通过正弦孔的占据情况直观显示出来。