Catalytic Epoxidation of Styrene over GO Supported Oxovanadium (IV) Complex:
Elucidating the Mechanistic Route through DFT Study
Ravi a
Vithalani , Dikin S. a
Patel , Chetan K. a
Modi *, Vaishali b
Sharma , Prafulla K. Jha b
aAppliedChemistry Department, Faculty of Technology & Engineering, The Maharaja Sayajirao University of Baroda, Vadodara-390 001, Gujarat, India
bDepartment of Physics, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara-390 002, Gujarat, India
[email protected], *[email protected]
1. Abstract & Objectives 2. Synthetic Strategy
OH OH
Catalytic epoxidation of olefins are of significant importance particularly in the pharmaceuticals O
COOH COOH H2N Si
O
and fine chemical industries and the epoxides are most versatile raw material in scores of organic O
OH
synthesis. Epoxidation of styrene using environmentally benign 30% H2O2 was carried out by HO
Modified Hummer's O HO
graphene oxide (GO) supported oxovanadium (IV) complex [VO(L)-f-GO where H2L = 2,4-
O
dihydroxy acetophenone]. The as-synthesized catalyst was characterized by various physico- method OH Toluene,
HOOC
chemical techniques such as Fourier-Transform Infrared (FTIR), electronic spectra, X-ray OH Reflux,
photoelectron spectroscopy (XPS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), N2 atm,
Brauner-Emmett-Teller (BET) results, Raman spectra, scanning electron microscope (SEM) and COOH OH 24 h
transmission electron microscopy (TEM). To avoid the unfavourable exposure of “inborn” water Graphite OH OH
Graphene oxide
produced during decomposition of H2O2, ethylene glycol was chosen as a selective high boiling
and potent hygroscopic solvent. The effect of H2O2 on to structural properties, binding
mechanism and electronic properties of the catalyst and substrate was examined using DFT HO O O OH HO OH HO OH NH2 NH2
study. Based on theoretical studies, the formation of metal-peroxo species was substantiated V
through resonance Raman and UV/Vis studies and the plausible mechanistic route for the O
N N N N
epoxidation of styrene to styrene oxide (SO) was elucidated. The effect of various experimental
parameters, like mole ratio, catalyst concentration, solvents, solvent amount, time, temperature Si Si
and oxidants were also inspected. This heterogeneous catalyst was exhibited excellent catalytic Si
OOO OOO
Si Si Si
activity with 99.2% styrene conversion and 98.7% SO selectivity. OOO OOO O OO O OO OH
We have sketched out the roadmap to perform the research work with the following main VOSO4·5H2O HO
objectives:
Synthesis of GO followed by modification of –OH groups with 3-triethoxysilylpropylamine
Reflux, methanol, Reflux, ethanol,
(TSPA) (A-f-GO) and to characterize by FTIR, XRD, Raman, TGA, SEM and TEM. OOO OOO N2 atmosphere, 24 h O OO O OO N2 atmosphere, 8 h
Synthesis of Schiff base grafted on A-f-GO [(L)n-f-GO] followed by covalent grafting of Si Si Si Si
VOSO4•2H2O [VO(L)-f-GO] and to characterize by the above said techniques. OOO OOO
To study the catalytic competence of as-synthesized catalysts over selective epoxidation of Si Si
N N N N
styrene to styrene oxide (SO) using environmentally benign 30% H2O2 and ethylene glycol as O
potent hygroscopic solvent. V
A computational study was performed to substantiate the formation of metal-peroxo (VOO•) HO O O OH HO OH HO OH
species and to elucidate plausible mechanistic route for the epoxidation of styrene to SO. NH2 NH2
VOL-f-GO (L)n-f-GO A-f-GO
3. Results & Discussion
EA χ S ω ΔNmax
3.1. Characterization (
b
Systems
Styrene
(eV)
-1.12
(eV)
2.64
μ (eV)
-2.64
η (eV)
3.76
(1/eV)
0.13
(eV)
0.92
(eV)
0.70
3.2. Catalytic Aptitude
)
VO-Catalyst 2.91 3.40 -3.40 0.49 1.02 11.79 6.93
Co-Catalyst 2.98 3.92 -3.92 0.94 0.53 8.17 4.17 Styrene Selectivity Selectivity Selectivity TOF (h-
Systems
Cu-Catalyst 3.05 3.91 -3.91 0.86 0.58 8.88 4.54 Conversion (%) (SO) (%) (BzH) (%) Others (%) 1)
Styrene+H2O2 1.06 3.65 -3.65 2.59 0.19 2.57 1.41
VO-
3.25 4 -4 0.75 0.66 10.66 5.33 Graphite 0 0 0 0 -
Catalyst+H2O2
Co-
3.08 4.06 -4.06 0.98 0.51 8.40 4.14 GO 0.3 100 0 0 -
Catalyst+H2O2
Cu-
3.16 4.02 -4.02 0.86 0.58 9.39 4.67 A-f-GO 0.5 100 0 0 -
Catalyst+H2O2
Calculated electron affinity (EA), electronegativity (χ), chemical potential (μ), global hardness (η) and
Mulliken charge transfer plots of pristine (left panel) and H2O2 over (a) styrene
softness (S), global electrophilicity index (ω), additional electronic charge (ΔNmax) of all considered Co-f-GO 28.97 20.59 26.47 44.12 61.90
(b) VO-catalyst (c) Co-catalyst and (d) Cu-catalyst (right panel). systems.
Cu-f-GO 69.15 24.83 15.17 59.99 39.94
VO-f-GO 83.17 28.18 10.18 61.63 245.52
Compound Metal %
VOL-f-GO 23.01 ppm
4. Conclusions 5. References
In conclusion, VO-f-GO catalyst was inspected over the selective epoxidation of styrene using 30% H2O2 as an environmentally benign oxidant and [1] R. Vithalani, D. Patel, C. K. Modi, N. N. Som, P. K. Jha, S. R. Kane, Diamond & Related Materials 2018, 90, 154-165.
ethylene glycol as a potent hygroscopic solvent to avoid the adverse effect of “inborn” water. Excellent catalytic activity was seen with 99.2% [2] M. D. Stoller, S. J. Park, Y. W. Zhu, R. S. Ruoff, Nano Lett. 2008, 8, 3498-3502.
conversion of styrene and 98.7% selectivity for SO. [3] J. K. Nam, M. J. Choi, D. H. Cho, J. K. Suh, S. B. Kim, J. Mol. Catal. A 2013, 370, 7-13.
In assistance with DFT studies, we calculated the affinity of H2O2 to styrene and the catalyst which demonstrated the highest affinity of H2O2 to VO-f- [4] B. Zhao, Z. Han, K. Ding, Angew. Chem. Int. Ed. 2013, 52, 2-47.
GO indicating to prefer this catalyst for this transformation which is also in good agreement with our experimental results. Based on binding energy [5] R. G. Parr, W. Yang, Oxford University Press: New York, 1989.
calculations, we proposed a plausible catalytic reaction pathway explaining the formation of key products SO and BzH on cleavage of C-H and C=C
[6] R. G. Pearson, J. Org. Chem. 1989, 54, 1423-1430.
bond.
The influences of distinct parameters like diverse catalysts, mole ratio, temperature, time, catalyst concentration, solvents, solvent amount and oxidant
[7] R. G. Parr, R. G. Pearson, J. Am. Chem. Soc. 1983, 105, 7512-7516.
have also been studied and we came out with the results that styrene conversion along with product distribution and selectivity were extensively [8] S. Gunasekaran, R. A. Balaji, S. Kumaresan, G. Anand, S. Srinivasan, Can. J. Anal. Sci. Spectro. 2008, 53, 149-162.
affected by the reaction variables. [9] B. Kosar, C. Albayrak, Spectrochim. Acta. A 2011, 78, 160-167.
For instance, TBHP favoured the production of BzH as a key product, however, if we look for SO as the key product then 30% H2O2 was to be [10] B. Tyagi, U. Sharma, R.V. Jasra, Appl. Catal. A, 2011, 408, 171-177
considered as a selective greener oxidant. Similarly, to avoid the adverse effect of producing water by the decomposition of H2O2 and for preventing
the acid formation, ethylene glycol was chosen as a high boiling and potent hygroscopic product selective solvent. This catalyst was recycled three 6. Acknowledgement
times without significant loss activity and this excellent performance of the catalyst could be due to the GO support and vigorous immobilization tactic.
Even though GO has shown excellent performance as a support yet it is a subject of great challenge to fabricate the sub-nano catalyst by an absolutely The authors warmly acknowledge to the Head, Applied Chemistry Department, Faculty of Technology & Engineering, The Maharaja Sayajirao University of
simple and greener route with immense performance. Baroda, Vadodara, Gujarat, India for providing the necessary laboratory facilities.
