zeolite confined nano-titania catalyst nailed down
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Zeolite Confined Nano-Titania Catalyst Nailed Down
Jian-jie Liang*1 , George Fitzgerald1, Istvan Halasz2
1Accelrys Inc. 2PQ Corporation
• Some highly active, hydrophilic, MFI structured titanium silicate catalysts are characterized by an intense UV absorption centered in the 213-233 nm range.
• The assignment of this band to a specific molecular structure has remained unclear.
• Time-Dependent Density Functional Theory (TD-DFT) to decipher the structural origin of this intermediate UV band.
Prologue
TS-1 Structure
• Si94Ti2O192
• Tendency of ordering by neutron diffraction (Lamberti, et. al., 2001)
• Hydrophobic
• Characteristic UV band @ 211 nm
180 200 220 240 260 280 300 320 340
Inte
nsity [
arb
itra
ry u
nits]
Wavelength [nm]
211 221
315
265
Isolated Tetrahedral Ti4+ Octahedral Ti4+
Hydrophilic Ti-MFI
• Hydrophilic
• More active and selective, even without
applying organic solvents
• Characteristic UV band @ 221 nm
180 200 220 240 260 280 300 320 340
Inte
nsity [
arb
itra
ry u
nits]
Wavelength [nm]
211 221
315
265
Isolated Tetrahedral Ti4+ Octahedral Ti4+
TD-DFT
Translate structural hypothesis to UV spectra
Time-dependent density functional theory
(TD-DFT) in DMol3
Delley, J. Phys.: Condens. Matter 22 (2010) 384208
Necessary to extend traditional ground-state DFT method to model phenomena involving excited states, such as in optical spectra.
Dealing with Large systems-QMMM
TD-DFT is Time-Consuming
− Typically, each excited state costs the
same as the ground-state SCF
− To be computationally tractable, only the
most chemically relevant portion of a
structure can be treated quantum
mechanically (QM-region)
− The rest of the chemical environment will
be treated using atomistic (classical)
modeling (MM-region)
QM-region
MM-region
Computational Details
• TDDFT limited to molecules
• QM/MM optimization of geometry followed by DMol3 TDDFT of QM region
– ~100 atoms in QM region
– QM region radially incremented until convergence in UV property
• MM region handled through GULP/Dreiding
• QM region by mechanical embedding
Configurations for full treatment
Computed UV spectra
180 200 220 240 260 280 300 320 340
Inte
nsity [
arb
itra
ry u
nits]
Wavelength [nm]
211 221
315
265
Isolated Tetrahedral Ti4+ Octahedral Ti4+
180 200 220 240 260 280 300 320 340
Inte
nsity [
arb
itra
ry u
nits]
Wavelength [nm]
211 221
315
265
Isolated Tetrahedral Ti4+ Octahedral Ti4+
Other configurations considered
Other configurations considered
Conclusions
• TDDFT calculations can yield UV spectra that agree well with experimental spectra on solid phases such as zeolite materials.
• Combined computational and experimental studies of the target MFI-structured titanium silicates indicate that a model containing tetrahedral Ti(OH)4 nanoparticles, not covalently bound to the framework, accounts for the enhanced catalytic activity of the material.
Experimental UV spectra
180 220 260 300 340 380
1 2 3
4 5
Wavelength [nm]
Ku
bel
ka-M
un
k A
bso
rban
ce [
arb
itra
ryu
nit
s]
202 221211
310
237
270
1,2: “good” TS-1
catalysts.
5: Typical ill-
synthesized material
with low catalytic
activity and
selectivity.
3,4: Transitions
between the good
and bad TS-1
products, containing
increasing amounts
of octahedral, non-
framework,
TixOy(OH)z
oligomers
UV spectra calculated for selected clusters
The Ti(OH)4 cluster (3rd structure from left above) gave a spectrum blue-shifted by ~
50 nm compared to when in the zeolite environment
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