Use of CuO encapsulated in mesoporous silica SBA-15 as ... · S1 Use of CuO encapsulated in...
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Use of CuO encapsulated in mesoporous silica SBA-15 as recycled catalyst for
allylic C–H bond oxidation of cyclic olefins at room temperature
Saadi Samadi*a, b, Akram Ashouria, Mehdi Ghambarianc
aLaboratory of Asymmetric Synthesis, Department of Chemistry, Faculty of Science, University of Kurdistan, Zip
Code 66177-15175, Sanandaj, Iran. E-mail: [email protected]
bResearch Centre of Nanotechnology, University of Kurdistan, P.O. Box 416, Sanandaj, Iran
cGas Conversion Department, Faculty of Petrochemicals, Iran Polymer and Petrochemical Institute, P.O. Box
14975-112, Tehran, Iran
Page List of contents
S1 Title, author’s name, address
S2 Typical procedure for preparation of SBA-15
S3 SEM of SBA-15
S4 EDX spectrum of SBA-15
S5 Typical procedure for functionalization of SBA-15 by 3-aminopropyltrimethoxysilane
S6 SEM of NH2-SBA-15
S7 EDX spectrum of NH2-SBA-15
S8 SEM of Cu-SBA-15
S9 EDX spectrum of Cu-SBA-15
S10 SEM of Cu-N-SBA-15
S11 Elemental mapping of the Cu-N-SBA-15 catalysts
S12 Mix elemental mapping of the Cu-N-SBA-15 catalysts
S13 EDX spectrum of N-Cu-SBA-15
S14 Typical procedure for synthesis of tert-butyl 4-nitrobenzoperoxoate
S15 IR of 1
S16 1H NMR of 1
S17 IR of 2
S18 1H NMR of 2
S19 IR of 3
S20 1H NMR of 3
S21 13C NMR of 3
S22 1H NMR of 4
S23 FT-IR of 4
S24 1H NMR of 5
S25 References
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2017
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1. Typical procedure for preparation of SBA-15
Mesoporous silica SBA-15 was prepared by a method that described in the literature. 2.0 g Pluronic P123
(Poly(ethylene glycol)-block-Poly(ethylene glycol)-block-Poly(ethylene glycol)-block) copolymer as a surfactant
was dissolved in 46 mL deionized water with 10ml concentrated HCl in a capped 100 mL Erlenmeyer flask at room
temperature. After complete copolymer dissolution (0.5-1h), solution of TEOS as a source of Si (4.6 gr) in
deionized water was added and the solution was stirred vigorously at 40 °C for 15 min, The solution was stirred for
an additional 10 minutes and Finally the mixture transferred into a stainless steel jacketed Teflon vessel and heated
at 100◦C for 48 h. the mixture was cooled to room temperature and solid product was separated by filtration followed
by washing with deionized water until pH=7-8 was achieved. Finally dried at 60°C . Template removal was
performed by calcination at 823 K for 6h. the XRD, SEM, BET, EDX and FT-IR results clearly demonstrated that
the mesoporous structure of SBA-15 [1].
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S3
Scanning electron micrograph of SBA-15
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EDX spectrum of the SBA-15
O K
SiK
keV
0
500
1000
1500
2000
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3000
3500
010
.00
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2. Typical procedure for Functionalization of SBA-15 by 3-Aminopropyltrimethoxysilane
Surface modification of SBA-15 was performed corresponding to the literature. Briefly, the dry mesoporous silica
materials (1g) were dispersed in 50 mL of dry toluene, then 2 mL of 3-Aminopropyltrimethoxysilane was added.
The resulting mixture was refluxed under nitrogen atmosphere for 24 h. The modified nonporous were collected
by filtration and washed thoroughly with CH2Cl2/CH3OH. Then soxhlet for 24h with CH2Cl2/CH3OH (1:1) to
remove any untethered species then the white solid NH2- SBA-15 dried at room temperature [2].
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Scanning electron micrograph of NH2-SBA-15
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S7
EDX spectrum of NH2-SBA-15
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Scanning electron micrograph of Cu-SBA-15
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EDX spectrum of the Cu-SBA-15
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Scanning electron micrograph of Cu-N- SBA-15
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Elemental mapping of the Cu-N-SBA-15 catalyst
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Mix elemental mapping of the Cu-N-SBA-15 catalyst
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S13
EDX spectrum of the N- Cu-SBA-15
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3. Typical procedure for Synthesis of tert-butyl 4-nitrobenzoperoxoate 1:
p-nitrobenzoyl chloride (3.2 g, 17.2 mmol) was dissolved in a 100 mL round bottom flask containing CH2Cl2 (35
mL). The solution was cooled to –20 °C and stirred under nitrogen for 15 min. Pyridine (1.7 mL, 20.0 mmol) was
added and the reaction mixture was stirred for 10 min. Then, tert-butyl hydroperoxide (3.5 mL, 20.0 mmol) was
added dropwise to the reaction at -20 °C, and stirred for 4 h. Then the reaction solution was diluted with CH2Cl2
(20 mL), and washed with water. The organic layer was separated, dried over MgSO4, and evaporated to obtained
crude yellow solid product. Purification using flash chromatography (90:10; n-hexane: EtOAc) afforded the light
yellow solid product 1. (3.9 g, 98% yield) [3, 4].
Tert-butyl 4-nitrobenzoperoxoate (1): Mp: 74-76°C (lit.75-78°C (ref. 3)); 1H NMR (300 MHz, CDCl3): H (ppm) =
1.45 (9H, s, Me), 8.17-8.40 (4H, m, Ar). 13C NMR (75 MHz, CDCl3): C (ppm) = 26.7, 84.5, 124.1, 131.3, 133.9,
150.6, 163.0.
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FT
-IR
of
per
est
er (
1)
NO2
OO
O
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S16
1H
NM
R o
f p
erest
er (
1)
NO2
OO
O
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S17
FT
-IR
of
com
po
un
d 2
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S18
1H
NM
R o
f co
mp
ou
nd
2
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S19
FT
-IR
of
com
po
un
d 3
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S20
1H
NM
R o
f co
mp
ou
nd
3
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S21
13C
NM
R o
f co
mp
ou
nd
3
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S22
13C
NM
R o
f co
mp
ou
nd
4
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S23
FT
-IR
of
co
mp
ou
nd
4
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S24
1H
NM
R o
f co
mp
ou
nd
5
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S25
References
1 D. Z hao, J. Feng, Q. Huo, N. Malosh, G. H. Fredrickson, B. F. Chmelka, G. D. Stucky,
Science, 1998, 279, 548-552
2 X. Zhang, E. Sau Man Lai, R. Martin-Aranda, K.L. Yeung, Appl. Catal. A: Gen., 2004,
261, 109-118.
3 S. Samadi, S. Nazari, H. Arvinnezhad, K. Jadidi, B. Notash, Tetrahedron 2013, 69, 6679-
6686.
4 S. Samadi, K.Jadidi, B. Khanmohammadi N. Tavakoli, J. Catal. 2016, 340, 344-353.