IN THE NAME OF GOD
Highly selective oxidation of benzyl alcohol to
benzaldehyde catalyzed by Zn-Fe2O4@ZnO coreshell nanostructures
Presenter:
Prof. Rahmatollah Rahimi
Magor student:
Mahdi Heidari-Golafzani
Introduction
Experimental
Results and
discussions
Conclusion
1
Introduction
Homogeneous
catalysis
Oxidation
Heterogeneous
catalysis
2
Homogeneous
catalysis
Benefits
 High activity and high selectivity
 Heat transfer and energy supply for reaction
Defects
 Purification of catalyst is difficult
 Recovery of catalyst is difficult
3
Heterogeneous
catalysis
Benefits
 Easy separation
 Reusability
4
Important of Zn-Fe2O4@ZnO
 Heterogeneous
 Magnetisablity
 Stability
 Easy synthesis
5
Schematic of reaction
6
Benzaldehyde





Precursor of pharmaceuticals
Precursor of plastic additives
Prepare of aniline dye malachite green
Precursor of certain acridine dyes
Prepare of cinnamaldehyde and styrene
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Experimental
Cat.
Alcohol
Acetonitrile
H2O2
80 ºC
8
Catalyst synthesis
Ethylene glycol
FeCl3.6H2O
ZnCl2
vigorous stirring
ammonium acetate
Foam
9
Catalyst synthesis
215 ºC
black precipitation
48 h
10
(Zn-Fe2O4)
Zn-Fe2O4 application
11
adsorption Curve
12
Zn-Fe2O4 analysis
XRD
VSM
13
SEM
422
400
220
511
440
311
01-073-1963
14
80
Magnetization (emu/gr)
60
40
20
0
-7500
-5500
-3500
-1500
500
-20
-40
-60
-80
Applied Field (Oe)
15
2500
4500
6500
̴ 120 nm
16
Catalyst synthesis
DI Water
Zn-Fe2O4
zinc acetate
NH3 (pH=11)
3 h, 120 ºC
24 h
Zn-Fe2O4@ZnO
17
80 ºC
Results and discussions
18
Zn-Fe2O4@ZnOanalysis
TEM
SEM
XRD
VSM
BET
19
SEM
̴ 150 nm
20
TEM
21
XRD
22
BET
23
VSM
76 emu/g
30 emu/g
24
catalyst
Zn-Fe2O4@ZnO
photocatalyst
25
Photocatalytic activity
26
Photocatalytic degradation curve
27
Catalytic activity
28
GC analyze
29
MASS analyze
30
Optimization
31
Evaluation
32
Comparision
Table 3. Comparison with other catalysts
a Reaction condition:(1mmol) catalyst, 80C, 1.5h, under 1 atm of molecular oxygen. Conversion and selectivity were
determined by GC-MASS using an intemal standard.
b Percent of conversion determined by GC-Ms.
c Percent of selectivity determined by GC-Ms.
d Benzhydrol (1 mmol), 70% TBHP (3 mmol), Cat. (10 mol%), temperature (70 ◦C).
e Benzyl alcohol (20.0 mmol), Cat. (10 mol%),30 wt% H O (33.0 mmol), temperature (70 ◦C).
2 2
f Benzyl alcohol (10.0 mmol), Cat. (1mol%), 30 wt% H O (10.0 mmol), temperature (75 ◦C).
2 2
33
Recyclability
34
Conclusion
High selectivity
Short reaction time
Heterogeneusly
Inviormentaly firendly
Good to excellent yield
Reusability
35
References
[1]. Burange, A. S., Kale, S. R., Zboril, R., Gawande, M. B., & Jayaram, R. V. (2014).
Magnetically retrievable MFe 2 O 4 spinel (M= Mn, Co, Cu, Ni, Zn) catalysts for oxidation of
benzylic alcohols to carbonyls. RSC Advances, 4(13), 6597-6601.
[2]. Yan, K., Wu, X., An, X., & Xie, X. (2013). Facile synthesis and catalytic property of spinel
ferrites by a template method. Journal of Alloys and Compounds, 552, 405-408.
[3]. Shi, F., Tse, M. K., Pohl, M.-M., Radnik, J., Brückner, A., Zhang, S., et al. (2008). Nano-iron
oxide-catalyzed selective oxidations of alcohols and olefins with hydrogen peroxide. Journal of
Molecular Catalysis A: Chemical, 292(1), 28-35.
[4]. Rahimi, R., Kerdari, H., Rabbani, M., & Shafiee, M. (2011). Synthesis, characterization
and adsorbing properties of hollow Zn-Fe 2 O 4 nanospheres on removal of Congo red from
aqueous solution. Desalination, 280(1), 412-418.
[5]. Rahimi, R., Heidari-Golafzani, M., & Rabbani, M. (2015). Preparation and photocatalytic
application of Zn-Fe 2 O 4@ ZnO core-shell nanostructures. Superlattices and
Microstructures.
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THE END
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