Supplementary Information for
Schiff base complex coated Fe3O4 nanoparticles: a highly
recyclable nanocatalyst for selective oxidation of alkyl aromatics
Lei Chen ● Bindong Li ● Dabin Liu
Nanjing University of Science and Technology, 210094 Nanjing, China
Results and Discussion
Benzene, acetonitrile, ethanol, water, and dichloromethane were used as
solvent to study the effects of solvent on the oxidation of ethylbenzene by
TBHP over Fe3O4/SiO2/Cu(II)salpr catalyst (Fig. S1). Acetophenone was
the major product in all reactions. The reaction had low conversion at the
presence of coordinating solvents such as ethanol, while using water as a
solvent made no reaction. As shown in Table S1, the maximum
ethylbenzene conversion decreased on different solvents in the following
order: 45% (benzene) > 32% (acetonitrile) > 28% (dichloromethane) >
20% (ethanol) > 0% (water). It seems that the donor electrons of these
solvents had more ability to occupy the vacant space around the existed
metal in catalyst, so this prevented coordinating from oxidant molecules
[1, 2]. Further investigations showed that the reaction in solvent free
condition had high selectivity and more catalytic activity. All the above

E-mail: libindong@mail.njust.edu.cn
showed that the ethylbenzene and solvents were competing for the active
sites of metal center on catalyst.
Scheme S1 shows a detailed mechanism of oxidation of ethylbenzene
based on the precedent literature for similar catalyst in hydrocarbon
oxidation by TBHP [2-5].
Captions:
Fig. S1 The influence of solvent on the ethylbenzene oxidation by
Fe3O4/SiO2/Cu(II)salpr catalyst.
Conversion/ Selectivity a (%)
Scheme S1 Detailed mechanism of oxidation of ethylbenzne.
100
83
Conversion
90
Selectivity
74
80
59
60
40
51
45
32
44
28
20
20
0 0
0
Solvent
Fig. S1 The influence of solvent on the ethylbenzene oxidation by
Fe3O4/SiO2/Cu(II)salpr catalyst. Conditions: catalyst (100 mg),
ethylbezene (20 mmol), TBHP (30 mmol), 80 oC for 8 h. (a Selectivity
toward the acetophenone.)
O-C-(CH3)3
H
O
2+
Cu
2+
(CH3)3-C-O-O-H
+
Cu OH
+
(CH3)3-C-O
Cu
(CH3)3-C-O
+
CH2 CH3
(CH3)3-C-OH
2+
Cu OH
2+
+
CH CH3
OH
C
H
OH
C
H
+
Cu
O
Cu
CH3
CH3 + (CH3)3-C-O
O
C
H
CH3 +
Cu OH
+
C
O
C
H
+
H2O
CH3
O
+
2+
Cu
+
CH3
2+
Cu
O
H
+
(CH3)3-C-OH
2+
2+
CH3
2+
OH
C
H
Cu OH
CH CH3
2+
+
Cu OH
+
H
O
+
OH
+
CH3OH
+
H2O
Scheme S1 Detailed mechanism of oxidation of ethylbenzne.
References
[1]
Uber JS, Vogels Y, Van Den Helder D, Mutikainen I, Turpeinen
U, Fu WT, Roubeau O, Gamez P, Reedijk J (2007) Eur J Inorg
Chem 26: 4197
[2] Habibi D, Faraji AR (2013) Appl Surf Sci 276:487
[3] Masteri-Farahani M (2008) J Mol Catal A: Chem 284:97
[4] Parida KM, Dash SS (2009) J Mol Catal A: Chem 306:54
[5] Arshadi M, Ghiaci M (2011) Appl Catal A: Gen 399:75