Atom-Selective Analyses Reveal the Structure-Directing Effect of Cs Cation on the Synthesis of Zeolites.

To understand the crystallization mechanism of zeolites, it is important to clarify the detailed role of the structure-directing agent, which is essential for the crystallization of zeolite, interacting with an amorphous aluminosilicate matrix. In this study, to reveal the structure-directing effect, the evolution of the aluminosilicate precursor which causes the nucleation of zeolite is analyzed by the comprehensive approach including atom-selective methods. The results of total and atom-selective pair distribution function analyses and X-ray absorption spectroscopy indicate that a crystalline-like coordination environment gradually forms around Cs cations. This corresponds to the fact that Cs is located at the center of the d8r units in the RHO structure whose unit is unique in this zeolite, and a similar tendency is also confirmed in the ANA system. The results collectively support the conventional hypothesis that the formation of the crystalline-like structure before the apparent nucleation of the zeolite.

[1]  K. Ohara,et al.  Structural Evolution of Amorphous Precursors toward Crystalline Zeolites Visualized by an in Situ X-ray Pair Distribution Function Approach , 2019, The Journal of Physical Chemistry C.

[2]  K. Ohara,et al.  Lepidocrocite-Type Titanate Formation from Isostructural Prestructures under Hydrothermal Reactions: Observation by Synchrotron X-ray Total Scattering Analyses , 2018, ACS omega.

[3]  J. Hu,et al.  Elementary Steps of Faujasite Formation Followed by in Situ Spectroscopy , 2018 .

[4]  I. Ivanova,et al.  Time-Resolved In Situ MAS NMR Monitoring of the Nucleation and Growth of Zeolite BEA Catalysts under Hydrothermal Conditions. , 2017, Angewandte Chemie.

[5]  V. Valtchev,et al.  Opening the Cages of Faujasite-Type Zeolite. , 2017, Journal of the American Chemical Society.

[6]  Andreas Menzel,et al.  Localization and Speciation of Iron Impurities within a Fluid Catalytic Cracking Catalyst. , 2017, Angewandte Chemie.

[7]  Y. Sasaki,et al.  Comparative Study on the Different Interaction Pathways between Amorphous Aluminosilicate Species and Organic Structure-Directing Agents Yielding Different Zeolite Phases , 2017 .

[8]  T. Yoshikawa,et al.  Structure-Directing Behaviors of Tetraethylammonium Cations toward Zeolite Beta Revealed by the Evolution of Aluminosilicate Species Formed during the Crystallization Process. , 2015, Journal of the American Chemical Society.

[9]  K. Ohara,et al.  Anomalous x-ray scattering studies of functional disordered materials , 2014 .

[10]  A. Corma,et al.  Synthesis Strategies for Preparing Useful Small Pore Zeolites and Zeotypes for Gas Separations and Catalysis , 2014 .

[11]  J. Rimer,et al.  Controlling crystal polymorphism in organic-free synthesis of Na-zeolites. , 2013, Journal of the American Chemical Society.

[12]  S. Hong,et al.  Synthesis of aluminosilicate and gallosilicate zeolites via a charge density mismatch approach and their characterization. , 2011, Journal of the American Chemical Society.

[13]  N. Azumi,et al.  Improvement in XAFS beamline BL01B1 at SPring-8 , 2009 .

[14]  S. Kohara,et al.  Changes in the medium-range order during crystallization of aluminosilicate zeolites characterized by high-energy X-ray diffraction technique , 2009 .

[15]  K. Tsutsumi,et al.  Synthesis of Cs-aluminosilicate zeolites and thermal phase transformation from BIK to CAS frameworks , 2009 .

[16]  S. Hong,et al.  The physical state of Ga species in Ga-containing mordenite zeolites , 2008 .

[17]  S. Billinge Nanoscale structural order from the atomic pair distribution function (PDF): There's plenty of room in the middle , 2008 .

[18]  S J L Billinge,et al.  PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals , 2007, Journal of physics. Condensed matter : an Institute of Physics journal.

[19]  Alfonso Pedone,et al.  A new self-consistent empirical interatomic potential model for oxides, silicates, and silica-based glasses. , 2006, The journal of physical chemistry. B.

[20]  M. Ogura,et al.  Phase selection of FAU and LTA zeolites by controlling synthesis parameters , 2006 .

[21]  A. Beale,et al.  Unraveling the crystallization mechanism of CoAPO-5 molecular sieves under hydrothermal conditions. , 2005, Journal of the American Chemical Society.

[22]  P. Cox,et al.  The hydrothermal synthesis of zeolites: Precursors, intermediates and reaction mechanism , 2005 .

[23]  Hiroshi Takahashi,et al.  Aluminosilicate Species in the Hydrogel Phase Formed during the Aging Process for the Crystallization of FAU Zeolite , 2003 .

[24]  P. Cox,et al.  The hydrothermal synthesis of zeolites: history and development from the earliest days to the present time. , 2003, Chemical reviews.

[25]  T. Proffen,et al.  Local structure of In0.5Ga0.5As from joint high-resolution and differential pair distribution function analysis , 1999, cond-mat/9911293.

[26]  A. Corma,et al.  Zeolites and Zeotypes as catalysts , 1995 .

[27]  Mark E. Davis,et al.  Mechanism of Structure Direction in the Synthesis of Si-ZSM-5: An Investigation by Intermolecular 1H-29Si CP MAS NMR , 1994 .

[28]  Raul F. Lobo,et al.  Zeolite and molecular sieve synthesis , 1992 .