Molecular Sieves SAPO-34 with Chabazite (CHA) Structure: Theoretical Study of Silicon Incorporation and Structural Properties

Hong Wang1, Yingxu Wei2, Cecil O¶Dell1, Zhongmin Liu2 and James P. Lewis1 1Department of Physics, West Virginia University, Morgantown, WV 2Dalian Institute of Chemical Physics, Dalian, P. R. China

³Zeolite´ is a broad term used to describe a family of microporous aluminosilicate minerals. Contain small pores and large surface area Constructed of AlO4-5 and SiO4-4 groups bound by oxygen Zeolites are synthesized by manipulating: 
   Structure Silica-Aluminum Ratio Pore Size Density

"Green Chemistry with Zeolite Catalysts." Chemical Engineering, The Chemical Engineers'Resource Page, Distillation, Heat Transer, Design, Spreadsheet Solutions, Departments, Chemistry. Web. 22 Apr. 2010. <>.

purification.replace phosphates as water softening agents Exchange Na in zeolite for Ca or Mg in water and separation Carbon dioxide separation Catalysis Shape-selective catalyst.on the basis of molecular diameter Acid catalysts ± used in the petrochemical industry Ion Exchange Detergent formulas.Application of Zeolite Materials Adsorption Drying.amazonaws.jpg .

Chang.pdf?auth=co&loc=en_US&id=46940&part=5 . C4«) Olefins Z-H: ZSM-5 catalytic zeolite 1977.tamu. Lang and Catalysis in Methanol to Olefins Conversion (MTO) Coal Natural Gas Synthesis Gas Methanol MTO Z-H +n(CH3OH) Z +H2O+olefin (C2. US patent 4062905 https://mailhost-2. C3.

SAPO-34: Microporous Silico-Aluminophosphate Molecular Sieve ZSM-5 SAPO-34 ZSM-5 ‡ Pore size around ‡ Strong acid sites ‡ Low selectivity in light olefins ‡ High selectivity Al Al Si Al P Al P Al P Al Al (Al-O)3-Si H O Al-(O-P)3 .

43nm C6H6 0.58nm ‡ ‡ ‡ ‡ Small size pores Suitable acid sites Strong stability High selectivity Al Al Si Al P Al P Al P Al Al (Al-O)3-Si H O Al-(O-P)3 .43n m C2H4 0.SAPO-34: Microporous Silicon Aluminumphospate Molecule Sieve SAPO-34 0.39nm C3H6 0.

Bao. X. Liu. X. H.SAPO-34: Crystallization Mechanism ‡ SM1: Al Si (not yield) ‡ SM2: P Si. R. Zhai. C. C.W. Z. H ‡ SM3: Al.Si Acidity: Si(4Al)<Si(3Al)<Si(2Al)<Si(1Al) Nonuniformed Silicon Incorporation J. M. X. Han. Microporous and Mesoporous Mateirals 53 (2002). Z.P Si. Q. Tan. He. Liu. 97 (108) .

Current Challenge of Silicon Incorporation in SAPO-34 Framework [AlPO4]+(n+m)Si4++(m-n)H+ [(n+m)Si.mP+mP5++nAl3+  Substantial computational time involved  Extensive possibilities of silicon incorporation into a larger framework  Identify optimal acid sites with a variety of silicon-incorporating environments  Unravel the puzzle of silicon incorporation trends during the SAPO-34 crystallization process and accompany the experimental design with a full-knowledge framework. .(m-n)H]nAl.

6 Al & 6 P Space Group: R3 [AlPO4]+(n+m)Si4++(m-n)H+ 2x2x2 supercell (288 atoms total) 96 tetrahedral (T) sites.mP+mP5++nAl3+ .(m-n)H]nAl.48 Al & 48 P Space Group: P1 (after silicon substitution) [(n+m)Si.SAPO-34 Computational Model and Goal Rhombohedral unit cell 12 tetrahedral (T) sites.

15 Å) in Si-O-Si configuration.1010 possible arrangements (C48/5*C48«.  6 Si¶s in 288 atoms supercell . sum over all Si neighbors of Si (choosing smallest Si cluster in supercell). .High Throughput Calculations ± Clustering  We investigate the properties of a non-uniformly distributed Si in a 2x2x2 AlPO-34 supercell.  Each 288 atom supercell optimization is approximately 10-12 hours.  For each Si in the supercell.  Clustering Factor ± root mean square from perfect Si-Si distance (3.  Generate high-throughput scenario from 100s of supercell calculations (a few 1000s are also feasible).)  Randomly distribute Si throughout the supercell and see what trends we can learn.

massively-parallel molecular-dynamics capabilities simulate 1000s of atoms   J. Jelinek et al. B. Rev. Phys. 1989-2007 (2011) . density-functional theory multi-center approximations Local ³excited" orbitals (fireball or Sankey-Niklewski orbitals) Atom in the box ± Fermi compression finite wavefunction Linear-scaling.. 195103 (2001) S. 1-15 (2003) P. 188. Rev. Phys. Lewis et al.D. Shellman et al. B. Lewis et al.P. J. 248.Fast Computational Approach to Evaluation of Material Properties and Chemical Reactivity: Ab initio DFT (FIREBALL)  Pseudopotentials. 64.P. B. Phys. 235101 (2005) J... Comp. Phys. Stat.. Sol. 64.

Clustering/Energy Correlation of 720 individual Structures 108 167 49 213 361 364 .

5P Si(4P). 4Si(4Al) all isolated .P Si.Low clustering factor.Si) pair substitution Al. 167 2 (Al. 49 structure No. structure No. but different energies«.

Clustering/Energy Correlation 108 167 49 213 361 364 .

213 structure No. 49 structure No. 364 2 (Al.Si) two pairs far away (2Al.P Si.Lower energy structure compared to smaller clustering factor structure No.Si) two pairs close 2 (Al.P Si. P) Si Si Si triplet .

Clustering/Energy Correlation 108 167 49 213 361 364 .

P) Si Si Si triplet 4 (P Si) Si(4Al) . 108 (2Al.Lower energy structure compared to larger clustering factor structure No. 364 structure No.

364 ..  In our low concentration incorporation (6 out of 96 possible sites).  Silicon substitution of Al. structure No.  Higher clustering factors mean that the silicon incorporation in the framework is spread throughout the entire supercell.What we see «. P pair is a common trend for our random silicon incorporation calculations and these pairs lower the binding energy. silicon prefers to form short range clusters.

 Design a computational route to also non-uniformly add hydrogen into the SAPO-34 framework based on current data and determine trends.  Increase silicon substitution concentrations and double SAPO-34 supercell to detect silicon incorporation trends (i.e. increasing the non-unformity)  Determine the acid site strengths for further CH3OH adsorption .Future Steps and Outline  Calculate the electrostatic potentials for our random networks to determine the affects introduced by silicon incorporation into the SAPO34 framework.

C Thank you! .R. Yingxu Wei Dalian Institute of Chemical Physics. Zhongmin Liu  Dr. P.Acknowledgements  WVU HPC Supercomputering Facility  Prof.

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