Synthesis of Zeolite Crystallites for Diffusion Measurement

• Applicant: Professor Dr. Jürgen Caro
• Subject Area: Physical Chemistry of Solids and Surfaces, Material Characterisation
• Term: from 2003 to 2012
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 5407656

• Final Report Year: 2011

Final Report Abstract

Several new synthesis routes for (i) zeolite crystals as model host systems for diffusion studies by the other partners of the consortium, and based on the molecular understanding of diffusion (ii) zeolite layers as gas separation membrane by crystallization on support surfaces have been developed. A good example to demonstrate this successful concept is the well-known zeolite structure LTA. First, huge single crystals of zeolite A as Na12[Si12Al12O48] in the LTA structure have been developed by modifying and improving the Charnell synthesis. The feedback of the diffusion studies in different time scales by the partners of the consortium using different methods gave as insight in the role of surface barriers and internal barriers on mass transport. This knowledge allowed us to crystallize LTA aluminium silicate as thin layer on a support with molecular sieve properties. However, this aluminium silicate LTA is hydrophilic and contains cations. So we developed new synthesis routs for cation-free hydrophobic LTA structures as aluminium phosphate and silicate/germinate. New templates like crown ether Kryptofix 222 had been found as structure directing agent. From diffusion studies we could again learn the properties of a corresponding molecular sieve layer on a support. By the end, the first aluminium phosphate and silicate/germinate molecular sieve membranes with LTA structure have been formed. The same concept has been used in MOF crystal and membrane formation.

Publications

• Adsorption and diffusion of alkanes in CuBTC crystals investigated using infra-red microscopy and molecular simulations. Micropor. Mesopor. Mater. 117 (2009) 22
  C. Chmelik, J. Kärger, M. Wiebcke, J. Caro, J.M. van Baten, R. Krishna
  
• Assessing surface permeabilities from transient guest profiles in nanoporous host materials. Angew. Chem. Int. Ed. 48 (2009) 3525
  D. Tzoulaki, L. Heinke, H. Lim. J. Li, D. Olson, J. Caro, R. Krishna, C. Chmelik
  
• Intracrystalline Transport Resistances in Nanoporous Zeolite X. ChemPhysChem 10 (2009) 2359
  A. Feldhoff, J. Caro, H. Jobic, J. Ollivier, C.B. Krause, P. Galvosas, J. Kärger
  
• Exploring the Nature of Surface Barriers on MOF Zn(tbip) by Applying IR Microscopy in High Temporal and Spatial Resolution. Micropor. Mesopor. Mater. 129 (2010) 340
  C. Chmelik, F. Hibbe, D. Tzoulaki, L. Heinke, J. Caro, J. Li, J. Kärger
  
• Molecular Sieve Membrane with Hydrogen Permselectivity: ZIF-22 in LTA Topology Prepared with 3-Aminopropyltriethoxysilane as Covalent Linker. Angew. Chem. Int. Ed. 49 (2010) 4958
  Huang, H. Bux, F. Steinbach, J. Caro
  
• Neutral and cation-free LTA-type aluminiumphosphate (AlPO4) molecular sieve membrane with hydrogen selectivity. JACS 132 (2010) 2140
  A. Huang, F. Liang, F. Steinbach, T.M. Gesing, J. Caro
  
• Steam-stable zeolitic imidazolate framework ZIF-90 membrane with hydrogen selectivity through covalent functionalization. JACS 132 (2010) 15562
  Huang, J. Caro
  
• Covalent Post-Functionalization of Zeolitic Imidazolate Framework ZIF-90 Membrane for Enhanced Hydrogen Selectivity. Angew. Chem. Int. Ed. 50 (2011) 4979
  Huang, J. Caro
  
• Highly oriented, neutral and cation-free AlPO4 LTA: from seed crystal monolayer to a molecular sieve membrane. ChemComm 47 (2011) 4201
  A. Huang, J. Caro