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

Results and discussions Introduction Experimental Results and discussions Conclusion

Homogeneous catalysis Heterogeneous catalysis Introduction Homogeneous catalysis Oxidation Heterogeneous catalysis

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

Heterogeneous catalysis Benefits Easy separation Reusability

Important of Zn-Fe2O4@ZnO Heterogeneous Magnetisablity Stability Easy synthesis

Schematic of reaction

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

Experimental H2O2 Cat. Alcohol Acetonitrile 80 ºC

Catalyst synthesis Ethylene glycol ZnCl2 FeCl3.6H2O vigorous stirring ammonium acetate Foam

Catalyst synthesis 215 ºC black precipitation (Zn-Fe2O4) 48 h

Zn-Fe2O4 application

adsorption Curve

Zn-Fe2O4 analysis XRD VSM SEM

01-073-1963 311 440 511 400 220 422

̴ 120 nm

Catalyst synthesis DI Water Zn-Fe2O4 zinc acetate NH3 (pH=11) 3 h, Zn-Fe2O4@ZnO

Results and discussions

Zn-Fe2O4@ZnO analysis TEM SEM XRD BET VSM

SEM ̴ 150 nm

TEM

XRD

BET

VSM 76 emu/g 30 emu/g

catalyst Zn-Fe2O4@ZnO photocatalyst

Photocatalytic activity

Photocatalytic degradation curve

Catalytic activity

GC analyze

MASS analyze

Optimization

Evaluation

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% 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

Conclusion High selectivity Short reaction time Heterogeneusly Inviormentaly firendly Good to excellent yield Reusability

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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