Diapositivo 1

1
THE UNIVERSITY of York
University of Aveiro
Preparation of Heterogeneous Catalysts for
Catalytic Epoxidation Reactions
Salete Balula
2
Which Catalysts?
Micelle Templated Silica Material
(MTS)
3
Preparation of Pyridine-3- Aminopropyl-MTS-MoO2Cl2
and ReCH3O3
Preparation of 3-Aminopropyl-MTS-MoO2Cl2(THF)
Characterization of the organomodified silica
catalysts
Catalytic activity of Pyridine-3-
Aminopropyl-MTS-MoO2Cl2
Catalytic activity of 3-Aminopropyl-MTS-MoO2Cl2(TH
F)
4
Preparation of Pyridine-3-Aminopropyl-MTS
5
Preparation of 3-Aminopropyl-MTS
6
Reaction of organomodified silica materials with
MoO2Cl2 or ReCH3O3 Under Argon
7
Characterization of Pyridine-3-
Aminopropyl-MTS-MoO2Cl2 or ReCH3O3
IR spectroscopy Raman Spectroscopy Microanalysis
C,H,N Nitrogen adsorption isotherms TGA Powder
X-ray diffraction What I still need to do? Mo
ICP analysis 29S CP MAS NMR 13C CP MAS NMR
Raman ?as 931 cm-1 vs
8
Characterization of Pyridine-3-
Aminopropyl-MTS-MoO2Cl2
IR spectroscopy Raman Spectroscopy Microanalysis
C,H,N Nitrogen adsorption isotherms TGA Powder
X-ray diffraction What I still need to do? Mo
ICP analysis 29S CP MAS NMR 13C CP MAS NMR
SBETm2g-1 538.80 Total Pore Volume ml/g
0.444
Loss of residual solvents
Desorption of attached organic groups
Disorded materials Mureseau et al., Langmuir
2005, 4648
9
Characterization of 3- Aminopropyl-MTS-MoO2Cl2
IR spectroscopy Raman Spectroscopy Microanalysis
C,H,N Nitrogen adsorption isotherms TGA Powder
X-ray diffraction What I still need to do? Mo
ICP analysis 29S CP MAS NMR 13C CP MAS NMR
1.57 mmol of ligand were found in 1g of material
SBETm2g-1 704.69 Total Pore Volume ml/g
0.565
10
Catalytic activity of Pyridine-3-
Aminopropyl-MTS-MoO2Cl2 In cyclooctene oxidation
reaction
Catalyst amount effect Cyclooctene amount
effect TBHP amount effect Temperature
effect Solvent effect
Selectivity 100
1.7 mmol Cyclooctene 2.7 mmol TBHP (in decane) T
55 ºC Different Catalyst amount
11
Catalytic activity of Pyridine-3-
Aminopropyl-MTS-MoO2Cl2 In cyclooctene oxidation
reaction
Different Cyclooctene amount 2.7 mmol TBHP (in
decane) T 55 ºC 43.8 mg Catalyst
Catalyst amount effect Cyclooctene amount
effect TBHP amount effect Temperature
effect Solvent effect
12
Catalytic activity of Pyridine-3-
Aminopropyl-MTS-MoO2Cl2 In cyclooctene oxidation
reaction
1.7 mmol Cyclooctene Different TBHP amount T
55 ºC 43.8 mg Catalyst
Catalyst amount effect Cyclooctene amount
effect TBHP amount effect Temperature
effect Solvent effect
13
Catalytic activity of Pyridine-3-
Aminopropyl-MTS-MoO2Cl2 In cyclooctene oxidation
reaction
1.7 mmol Cyclooctene 2.7 mmol TBHP (5.5 M in
decane) Different temperature reaction 43.8 mg
Catalyst
Catalyst amount effect Cyclooctene amount
effect TBHP amount effect Temperature
effect Solvent effect
14
Catalytic activity of Pyridine-3-
Aminopropyl-MTS-MoO2Cl2 In cyclooctene oxidation
reaction
1.7 mmol Cyclooctene 2.7 mmol TBHP (5.5 M in
decane) T 55 ºC 43.8 mg Catalyst
Catalyst amount effect Cyclooctene amount
effect TBHP amount effect Temperature
effect Solvent effect
15
Catalytic activity of Pyridine-3-
Aminopropyl-MTS-MoO2Cl2
3.5 mmol Cyclooctene 11 mmol TBHP T 80 ºC 90 mg
catalyst
3.5 mmol Cyclooctene 11 mmol TBHP T 55 ºC 90 mg
catalyst
Stability
Re-usability
Solid catalyst was filtred
The catalyst does not lose the activity in these
experimental conditions. The same conversion data
was achieved after 3 h of reaction.
16
Catalytic activity of Aminopropyl-MTS-MoO2Cl2(THF)
In cyclooctene oxidation reaction
Stability
Selectivity 100
3.5 mmol Cyclooctene 11 mmol TBHP T 55 ºC 90 mg
catalyst
7.5 mmol Cyclooctene 11 mmol TBHP T 55 ºC 90 mg
catalyst
In the presence of half amount of substrate, the
catalyst achieved almost the same conversion
data, after 24h of reaction.
17
Mechanism for epoxidation reaction with TBHP
18
Conclusions

• Pyridine catalyst showed higher stability than
  aminopropyl catalyst.
• After 3h of reaction, the same conversion data is
  achieved for the second
• and the third run of the pyridine catalyst.

Future Work
1- Finish the characterization of the catalysts
(NMR and ICP) 2- Study the oxidation of other
substrates (essencially limonene and pinene) 3-
Study the catalytic activity of MTS-MTO and Pd
supported complex.
Thank you
Duncan Macquarrie James Clark