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

Hong Wang1, Yingxu Wei2, Cecil ODell1, Zhongmin Liu2 and James P. Lewis1 1Department of Physics, West Virginia University, Morgantown, WV 2Dalian Institute of Chemical Physics, Dalian, P. R. China

Introduction
Zeolite 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. <http://www.cheresources.com/zeolitezz.shtml>.

Application of Zeolite Materials

Adsorption Drying, purification, 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- replace phosphates as water softening agents Exchange Na in zeolite for Ca or Mg in water

http://s3.amazonaws.com/memebox/uploads/3562/kanatzidis-gasNorthwester.jpg

Zeolite Catalysis in Methanol to Olefins Conversion (MTO)

Coal

Natural Gas

Synthesis Gas

Methanol
MTO

Z-H +n(CH3OH)

Z +H2O+olefin (C2, C3, C4)

Olefins

Z-H: ZSM-5 catalytic zeolite 1977, Chang, Lang and Silvestri, US patent 4062905

https://mailhost-2.tamu.edu/service/home/~/Zeolite_seminar.pdf?auth=co&loc=en_US&id=46940&part=5

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

SAPO-34: Microporous Silicon Aluminumphospate Molecule Sieve

SAPO-34

0.43n m

C2H4 0.39nm C3H6 0.43nm 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

SAPO-34: Crystallization Mechanism

SM1: Al Si (not yield) SM2: P Si, H SM3: Al,P Si,Si Acidity: Si(4Al)<Si(3Al)<Si(2Al)<Si(1Al) Nonuniformed Silicon Incorporation

J. Tan, Z. M. Liu, X. H. Bao, X. C. Liu, X.W. Han, C. Q. He, R. Z. Zhai, Microporous and Mesoporous Mateirals 53 (2002), 97 (108)

Current Challenge of Silicon Incorporation in SAPO-34 Framework

[AlPO4]+(n+m)Si4++(m-n)H+ [(n+m)Si,(m-n)H]nAl,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.

SAPO-34 Computational Model and Goal

Rhombohedral unit cell 12 tetrahedral (T) sites- 6 Al & 6 P Space Group: R3 [AlPO4]+(n+m)Si4++(m-n)H+

2x2x2 supercell (288 atoms total) 96 tetrahedral (T) sites- 48 Al & 48 P Space Group: P1 (after silicon substitution) [(n+m)Si,(m-n)H]nAl,mP+mP5++nAl3+

High Throughput Calculations Clustering

 We investigate the properties of a non-uniformly distributed Si in a 2x2x2 AlPO-34 supercell.  6 Sis in 288 atoms supercell - 1010 possible arrangements (C48/5*C48.)  Randomly distribute Si throughout the supercell and see what trends we can learn.  Clustering Factor root mean square from perfect Si-Si distance (3.15 ) in Si-O-Si configuration.  For each Si in the supercell, sum over all Si neighbors of Si (choosing smallest Si cluster in supercell).  Each 288 atom supercell optimization is approximately 10-12 hours.  Generate high-throughput scenario from 100s of supercell calculations (a few 1000s are also feasible).

Fast Computational Approach to Evaluation of Material Properties and Chemical Reactivity: Ab initio DFT (FIREBALL)


Pseudopotentials, density-functional theory multi-center approximations Local excited" orbitals (fireball or Sankey-Niklewski orbitals) Atom in the box Fermi compression finite wavefunction Linear-scaling, massively-parallel molecular-dynamics capabilities simulate 1000s of atoms

J.P. Lewis et al., Phys. Rev. B. 64, 195103 (2001) S.D. Shellman et al., J. Comp. Phys. 188, 1-15 (2003) P. Jelinek et al., Phys. Rev. B. 64, 235101 (2005) J.P. Lewis et al., Phys. Stat. Sol. B. 248, 1989-2007 (2011)

Clustering/Energy Correlation of 720 individual Structures

108 167

49

213

361 364

Low clustering factor, but different energies.

structure No. 49 structure No. 167

2 (Al,P Si,Si) pair substitution

Al,5P

Si(4P), 4Si(4Al) all isolated

Clustering/Energy Correlation

108 167

49

213

361 364

Lower energy structure compared to smaller clustering factor

structure No. 49 structure No. 213 structure No. 364

2 (Al,P Si,Si) two pairs close

2 (Al,P Si,Si) two pairs far away

(2Al, P)

Si

Si Si triplet

Clustering/Energy Correlation

108 167

49

213

361 364

Lower energy structure compared to larger clustering factor

structure No. 364 structure No. 108

(2Al, P)

Si

Si Si triplet

4 (P

Si)

Si(4Al)

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

Future Steps and Outline

 Calculate the electrostatic potentials for our random networks to determine the affects introduced by silicon incorporation into the SAPO34 framework.  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

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

Thank you!