Li Xinyu, Han He, Xu Wenqian, Hwang Son-Jong, Shi Zhichen, Lu Peng, Bhan Aditya, Tsapatsis Michael
Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455, United States.
State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning Province, China.
J Am Chem Soc. 2022 Jun 1;144(21):9324-9329. doi: 10.1021/jacs.2c01022. Epub 2022 May 17.
Low-silica faujasite (FAU) zeolites (with Si/Al ratio of ca. 1.2-1.8) sustain framework integrity and porosity upon moderate ion exchange (0.01 M NHNO solution for 1 h at ambient temperature), which introduces two kinds of protons, distinctive in reactivity and coordination to the zeolite framework, within supercages (H). Moderate ion exchange limited within supercages transpires while maintaining full occupancy of Na cations within associated sodalite cages; this in turn helps stabilize the framework of low-silica H-FAU zeolites. Protons located on site II (H) and site III (H) within supercages on low-silica FAU zeolites can be classified and enumerated by virtue of infrared spectroscopy, providing an opportunity to compare reactivities of these distinct protons for monomolecular protolytic reactions of propane. Protons on site II exhibit prominently higher reactivity for monomolecular propane dehydrogenation and cracking than protons on site III. Low-silica proton-form FAU zeolites (zeolite X) upon moderate ion exchange possess protons on site III that are unavailable on high-silica FAU zeolites (zeolite Y) and limit ion exchange within supercages, providing unprecedented high-temperature structural and chemical stability (>773 K) and enabling their application as solid-acid catalysts.
低硅八面沸石(FAU)分子筛(硅铝比约为1.2 - 1.8)在适度离子交换(0.01 M硝酸铵溶液,室温下1小时)后能保持骨架完整性和孔隙率,这会在超笼(H)内引入两种质子,它们在与沸石骨架的反应性和配位方面存在差异。在超笼内进行的适度离子交换过程中,相关方钠石笼内的钠离子保持完全占据状态;这反过来有助于稳定低硅氢型八面沸石(H - FAU)的骨架。低硅八面沸石超笼内位于II位(H)和III位(H)的质子可通过红外光谱进行分类和计数,这为比较这些不同质子对丙烷单分子质子分解反应的反应性提供了机会。II位质子对单分子丙烷脱氢和裂解的反应性明显高于III位质子。适度离子交换后的低硅质子型八面沸石(X型沸石)在III位拥有高硅八面沸石(Y型沸石)所没有的质子,并限制了超笼内的离子交换,从而提供了前所未有的高温结构和化学稳定性(>773 K),并使其能够用作固体酸催化剂。