IN THE NAME OF GOD

Highly selective oxidation of benzyl alcohol to benzaldehyde catalyzed by Zn-Fe2O4@ZnO core-

shell nanostructures

Presenter:Prof. Rahmatollah Rahimi

Magor student:

Mahdi Heidari-Golafzani

Introduction

Experimental

Results and discussions

Conclusion

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Oxidation

Homogeneous catalysis

Heterogeneous catalysis

2

Introduction

BenefitsHigh activity and high selectivityHeat transfer and energy supply for reaction

DefectsPurification of catalyst is difficultRecovery of catalyst is difficult

Homogeneous catalysis

3

BenefitsEasy separationReusability

Heterogeneous catalysis

4

HeterogeneousMagnetisablityStabilityEasy synthesis

Important of Zn-Fe2O4@ZnO

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Schematic of reaction

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Precursor of pharmaceuticals Precursor of plastic additives Prepare of aniline dye malachite green Precursor of certain acridine dyes Prepare of cinnamaldehyde and styrene

Benzaldehyde

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8

Experimental

Cat. Alcohol Acetonitrile H2O2

80 ºC

Catalyst synthesis

9

FeCl3.6H2O ZnCl2

Ethylene glycol

vigorous stirring

ammonium acetateFoam

Catalyst synthesis

10

black precipitation

(Zn-Fe2O4)

215 ºC

48 h

11

Zn-Fe2O4 application

adsorption Curve

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Zn-Fe2O4 analysis

13

XRD VSM SEM

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01-073-1963

311

220 400

440

422

511

15

16

1 120 nm

Catalyst synthesis

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Zn-Fe2O4 zinc acetate

(pH=11)

120 ºC

Zn-Fe2O4@ZnO

80 ºC

DI Water

3 h, 24 h

NH3

Results and discussions

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XRDSEM TEM

BET VSM

Zn-Fe2O4@ZnO analysis

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SEM

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1 150 nm

TEM

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XRD

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BET

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VSM

24

76 emu/g

30 emu/g

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Zn-Fe2O4@ZnO

catalyst

photocatalyst

Photocatalytic activity

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Photocatalytic degradation curve

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Catalytic activity

GC analyze

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MASS analyze

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Optimization

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Evaluation

Comparision

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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% H2O2 (33.0 mmol), temperature (70 ◦C). f Benzyl alcohol (10.0 mmol), Cat. (1mol%), 30 wt% H2O2 (10.0 mmol), temperature (75 ◦C).

Recyclability

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High selectivityShort reaction timeHeterogeneuslyInviormentaly firendlyGood to excellent yieldReusability

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Conclusion

[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.

References

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THE END

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