Visible-light-driven photochemical activity of ternary Ag/AgBr/TiO2nanotubes for oxidation C(sp3)-H and C(sp2)-H bonds

Article abstract of DOI:10.1039/d0nj03907a

The Ag/AgBr/TiO2 ternary component nanotube as a heterogeneous photocatalyst was used for the solvent-free oxidation of the benzylic C(sp3)-H bond to the corresponding carbonyl compound or the solvent-controlled selective oxidative cleavage of the CC double bond of styrene to benzaldehyde under visible light at room temperature. A wide variety of carbonyl compounds were successfully synthesized through the developed photocatalytic process. Several advantages such as solvent-free conditions, sans additional oxidant, simple reaction, short reaction time, and easy separation of the product promote the reaction to be green. Moreover, the Ag/AgBr/TiO2 nanotubes could be used several times without reduction in their photocatalytic activity. This journal is

Full text of DOI:10.1039/d0nj03907a

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ISSN 1144-2546
PAPER
Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
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Visible-Light Driven Photochemical activity of ternary
3
2
Ag/AgBr/TiO Nanotubes for Oxidation C(sp )-H and C(sp )-H Bonds
2
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
Mona Hosseini-Sarvari,* Abdulhamid Dehghani
DOI: 10.1039/x0xx00000x
2
Ag/AgBr/TiO ternary component nanotube as a heterogeneous photocatalyst was used for the solvent-free oxidation of
3
benzylic C(sp )-H bond to the corresponding carbonyl compound or the solvent-controlled selective oxidative cleavage of
C=C double bond of styrene to benzaldehyde under visible light at room temperature. A wide variety of carbonyl compounds
were successfully synthesized through the developed photocatalytic process. Several advantages such as solvent-free
conditions, no additional oxidant, simple, and short reaction time, and easy separation of product, promote the reaction to
be green. Moreover, the Ag/AgBr/TiO
2
nanotubes can be used several times without reducing its photocatalytic activity.
visible light, owing to surface plasmonic resonance (SPR). The surface
plasmon resonance occurs when the frequency of the transmitted
Introduction
light equals the frequency of the plasma. Hence, the plasma
2
Titanium dioxide (TiO ) has been widely used as a heterogeneous
frequency is drawn to the ultraviolet region, so it can be said that
photocatalyst for degradation and deactivation of bacteria and
cancer cells since 1985 as a semiconductor due to its abundance and
non-toxicity.1-3 Besides, titanium dioxide is used for wastewater
treatment, degradation of various pollutants, and other items due to
chemical stability and low cost.4-5 However, titanium dioxide is
considered to be defective due to the high bandgap (3.2 eV),
quantum yield loss, and lack of absorption of visible light.6-10
Although titanium dioxide absorbs ultraviolet light, it should be
noted that only 5% of the sun's energy contains ultraviolet light.
Therefore, this catalyst should be modified to increase photoactivity
and eliminate the defects mentioned. Hence, several studies have
been done to address these deficiencies, strategies such as doping
these metals reflect the light in the visible region.20-29 As a
consequence, Ag/AgX has been found an impressive and stable
photocatalyst under visible light irradiation. To overcome the limited
ability of TiO to absorb visible light, and on the other hand, to
2
-
+
increase the stability and facilitating electron-hole (e /h ) separation,
3
0-38
a composite based on Ag/AgBr and TiO has been studied.
2
One of the challenges that remain much interested in organic
3
chemistry is the functionalization of unreactive C(sp )-H bonds. High
3
bond dissociation energy C(sp )-H bonds, makes it very difficult and
elegant to be functionalized. By investigating the structure of many
commercial drugs, we conclude that many of them contain one or
more oxidized benzylic position. 39-41(Figure 1)
with noble metals, coupling with non-metals, and sensitization have
been proposed.11-14
Commonly, in drug discovery, these drugs are generated by oxidation
of C-H benzylic bonds using strong oxidant, biomimetic metal
complex, or cytochrome p450. However, these methods are highly
precious because of using expensive catalyst systems and are also
limited to use hazardous reagent, toxic oxidants, and are not good
for scale-up.42-45
Silver halides are known as light-sensitive materials and are not
usually used in photocatalytic reactions because of their instability
against light radiation. When the silver halide was irradiated with a
light, a positive hole was created in the silver-halide due to releasing
an electron. Then, the released electron was absorbed by a silver ion,
results in the separation of a silver atom. The process was followed
by the re-absorption of light by silver-halide and forms a cluster of
silver atoms. The formation of this cluster does not usually allow
silver halide to be used in photocatalytic reactions alone.15-19
According to our research topic and many published papers,
plasmonic noble metals such as Ag, Au, and Pd render remarkable
2
Today, O has attracted a lot of attention because of its low cost. It
should be mentioned that the oxidation process in the presence of
molecular oxygen as the oxidants, usually performs in the aqueous
media. The most important challenge of the use of water as the
2
reaction solvent for oxidation with O is the low solubility of gases in
the aqueous media, however, the green chemistry concepts offer the
use of it instead of the toxic organic solvent due to its environmental
compatibility.39-50 However, replacement of molecular O
oxidant was a way to improve the reaction conditions that transition
with toxic
a. Department of Chemistry, Shiraz University, Shiraz 7194684795, I.R. Iran
. Corresponding author, Email address: hossaini@shirazu.ac.ir
Electronic Supplementary Information (ESI) available: See DOI: 10.1039/x0xx00000x
2
†
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metal catalysts, additives, high temperature, and toxic solvents were
still required.51-53
including gold nanoparticles and mesoporous silica VnieawnoArptiaclretOicnlleinse.
DOI: 10.1039/D0NJ03907A
This surfactant is of great importance in the synthesis of
nanoparticles that regulates the properties of nanoparticles by
controlling the size and shape of nanoparticles. Other applications
CTAB include adsorption on nanoparticles and reducing surface
energy. It can also be used to prevent aggregation e.g. via DLVO
mechanisms.73-75
O
H
N
O
N
Cl
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Bupropion
a-Pyrrolidinopentiophenone
O
In this report, Ag /AgBr /TiO as an efficient, reusable, and effective
2
3
photocatalyst was used for photo oxygenation of benzylic C(sp )-H
O
CH3
O
O
2
OH
and C(sp )-H using molecular O
2
(no oxidant) in the presence of
N
O
visible light irradiation at room temperature. A wide verity of
carbonyl compounds successfully synthesized through the oxidation
of C-H benzylic or cleavage of C=C double bond in the solvent-free or
solvent-controlled systems, respectively. Moreover, the oxidation of
C=C of α-methyl styrene (AMS) as a model reaction for the
compounds with an alkyl substitute at the α-position of their double
bond. The developed method showed some characteristic
advantages, for instance, green solvent-free oxidation of C-H
benzylic, selective oxidation of C=C double bond of styrene to
benzaldehyde, no requirement to oxidant, simple and short reaction
time and easy separation of products, promoting the reaction to it
will be the green chemistry twelve principles. In this context, to show
the uniqueness, advantages, and novelty of our work, an overview of
Donepezil
Ketoprofen
Figure 1. The chemical structures of some commercial drugs
contain one or more oxidized benzylic position.
Besides, the synthesis of carbonyl compounds of olefins in chemical
reactions including in the industry is very valuable, because,
oxygenated compounds such as benzaldehyde as an artificial
intermediate in chemical and pharmaceutical industries can be used
including pigment production, perfume, flavors, additives, and hair
dyes.54-60 The production of aldehydes from carbon-carbon double
bonds is very valuable, but it should be taken into account due to the
oxidation resistance of the alkenes but their products are more
susceptible to oxidation and factors like the catalyst, solvent, oxidant
should be considered.61,62 Homogeneous catalysts are more efficient
at oxidation than heterogeneous catalysts and can be used to analyze
and study reaction mechanisms, also, compared to heterogeneous
catalysts, they have well-defined active sites, but because of their
high sensitivity to reaction conditions, and their relatively difficult
separation from the product mixture, catalytic recovery is difficult.
but due to the relatively poor thermal stability and high cost of
catalyst recycling due to difficult catalytic recovery, we go to
heterogeneous catalysts.63-66 Although there are many methods for
the oxidation of unsaturated hydrocarbons today, the following
three methods are more common and well-known than others: (1)
Ozonolysis of olefins to ozonides and conversion to aldehydes or
ketones, (2) cleavage of C=C bond on substances such as tetraoxide
3
2
the reported catalysts for the oxidation of C(sp )-H and C(sp )-H
bonds were provided in Table S1 (see SI). Although the reported
catalysts have advantages, they catalyzed only one of the oxidation
3
2
of C(sp )-H or C(sp )-H bonds, however, our developed photocatalyst
can catalyze the oxidation of both C(sp )-H and C(sp )-H bonds which
makes it suitable for potential practical applications compared to
reported catalysts. Regarding oxidation of C(sp )-H bond, as shown
in this Table (Table S1), most of the reported catalysts perform the
3
2
3
3
oxidation of C(sp )-H bond in the presence of an oxidant such as O
(1-27 atm), O , hydrogen peroxide, and TBHP. Moreover, these
2
3
catalytic reactions need to use an organic solvent such as AcOH,
pyridine, THF, and so on. While our developed photocatalyst
performs the oxidation of C(sp )-H bond in solvent-free conditions
without needing any oxidant under irradiation of blue-light which are
significant advantages for the developed catalytic process in a green
chemistry point of view. Moreover, the reported photocatalytic
3
acid and ruthenium tetraoxide, and (3) Oxidation of olefinic
compounds by hydrogen peroxide.67 Although the industry today
3
methods need to use CH CN/HCl as the solvent for the oxidation
uses the process of chlorohydrin for the oxidation of unsaturated
hydrocarbons, we should know that all the mentioned methods have
defects including waste generation and environmental
incompatibility, catalyst recovery and recycling problems, negative
impact on product quality and the use of metal oxides and salts as
oxidants is not common. It should be noted that the previous reports
in the literature were covered the production of benzaldehyde
through the oxidation of benzyl alcohols, styrene oxidation in the
while the developed method is under solvent-free condition,
indicating an improvement in the reaction conditions via developing
2
a green photocatalytic pathway. In the case of C(sp )-H bond
oxidation, the developed method shows significant advantages such
as aerobic oxidation, performing the oxidation at ambient
temperature which makes it high throughput and easy to scale-up
compared to the reported methods.
2
supercritical carbon dioxide (scCO ) /PEG biphasic catalytic system
using PdCl catalyst or by olefin oxidation in THF with the help of N-
2
heterocyclic carbine Pd (II) complex.58, 68-72
Hexadecyl(trimethyl)ammonium bromide (CTAB) is used as a type
quaternary ammonium surfactant in the synthesis of nanoparticles,
2
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diluted with EtOAc and centrifuged to recycle the photVoiecwatAartlicylsetO. nTlhinee
filtrate was extracted with EtOAc and waterD.OTIh: e10o.1r0g3a9n/Dic0lNaJy0e3r9w07aAs
dried with Na SO , concentrated under vacuum, and purified using
2 4
column chromatography on silica gel (petroleum ether: ethyl
acetate, 10:1 V/V) to afford the pure product.
Experimental Section
General
All chemicals were either prepared in our laboratories or were
purchased from Fluka, Aldrich, Acros, and Merck, and all solvents
were obtained from commercial sources and if needed were purified
using standard methods. Field Emission Scanning Electron
Microscopy was recorded on FESEM, Nova Nanosem450.
Transmission electron microscopy (TEM) images were recorded
using a Philips EM 208S instrument with an accelerating voltage of
2
Photocatalytic oxidative C(sp )-H bonds
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.01 g Ag/AgBr/TiO
2
nanotubes as the photocatalyst and 3 mmol
styrene derivatives were added to 1 mL CH
3
CN. The mixture was
stirred under CFL White 15 W at room temperature in the air
atmosphere until the reaction was completed (monitored by TLC).
After that, the photocatalyst was separated from the product by
centrifugation and extraction with EtOAc and water. The organic
1
00 kV. The Brunauer- Emmett-Teller (BET) surface area analysis was
adopted at 77 K to obtain surface areas with the flow of N . The
fluorescence spectrum of the as-synthesized catalyst was recorded
by spectrofluorometer (Perkin-Elmer model: LS45). X-ray
2
2 4
layer was dried over anhydrous Na SO and concentrated under
vacuum. The residue was purified by column chromatography on
silica gel (petroleum ether: ethyl acetate, 10:1 V/V) to afford the pure
product.
a
diffraction (XRD) patterns of catalysts were recorded by the Bruker
AXS D8-advance X-ray diffractometer using CuKα radiation
(λ=1.54178 Å) with scanning range 2θ from 20 to 70 . UV–Vis
absorption spectrum was measured by the UV–Vis Results and discussion
spectrophotometer (V_670-JASCO, Japan) with an integrating sphere
attachment. PerkinElmer FT-IR spectrophotometer Model Spectrum Optical properties of Ag/AgBr/TiO nanotubes
RXI was applied to FT-IR measurement using KBr pellets. Rigaku
o
o
2
2
D/max-3C (Japan) with Cu-Kα (λ = 1.54 nm) radiation powder was At first, to find the optical specification of synthesized Ag/AgBr/TiO ,
used for EDX analysis. A Bruker advanced DPX-250 spectrometer was the UV-Vis and fluorescence measurements were expert and the
applied to take NMR spectra in CDCl
operating for 13C at 62.9, 70, acquired spectra are shown in Figure 2. The UV-vis spectrum of
and 100 MHz and for 1H at 250, 300, and 400 MHz. The lamps for Ag/AgBr/TiO nanotubes (Figure 2a) exhibited a visible light
irradiation were a compact fluorescent lamp (CFL) 15 W white, blue absorption peak at 325 nm related to the direct bandgap of AgBr. The
3
2
LED 12 W, a green LED 12 W and a red LED 12 W.
2
absorption peak at 277 nm can be assigned to TiO . The absorption
band at 460-800 nm can be assigned to the surface plasmon
absorption (SPR) of silver. Figure2b shows the photoluminescent
Preparation of Ag/AgBr/TiO2
spectra of TiO NPs (P25) and Ag/AgBr/TiO
) was dissolved in photocatalyst. As shown in this Figure, the TiO
2
2
2
nanotubes
NPs reveals an
In a typical procedure, 0.5 g quantity of P-25 (TiO
2
5
0.0 mL distilled water, which was sonicated for 30 minutes followed emission wavelength at 573 nm, which is consisted of the previously
by adding 0.6 g of hexadecyltrimethylammonium bromide (CTAB). reported spectra for the TiO
(P25).76,77 When the Ag/AgBr was
Afterward, the reaction mixture was stirred magnetically for about doped in the TiO NPs structure, the emission wavelength of TiO
0 minutes. The synthesis process was followed by the rapid addition (P25) was shifted to 615 nm due to the SPR of the Ag atoms.
of 0.1 g silver nitrate and 1.10 mL of ammonium hydroxide (25 wt % Moreover, the PL intensity of the Ag/AgBr/TiO nanotubes
NH ) to the reaction mixture. Using of CTAB in the synthesis of photocatalyst is characteristically lower than the unmodified TiO
Ag/AgBr/TiO nanotubes exhibited two interest advantages as (P25), indicating the successful doping the Ag/AgBr in the TiO
2
2
2
3
2
3
2
2
2
1
7
reported in the literature ; (I) at alkaline condition, CTAB has a structure.
positive charge, therefore, cationic CTAB could be adsorbed on the
TiO surface, leading to homogeneously dispersed AgBr due to
2
limiting the amount of nucleation sites for the producing AgBr metal
a) 1.4
2
75 nm
325 nm
1
1
0
.2
.0
.8
+
island. (II) CTAB could provide bromide ions to precipitate Ag as
AgBr. Then the reaction mixture was stirred for 16 hours at ambient
temperature. The product was filtered and washed three times with
deionized water, dried at 70 °C for 12 hours in an oven, and finally,
calcined at 500 ° C for 3 h.17
0.6
0.4
0.2
0.0
4
60-800 nm
3
Photocatalytic oxidative C(sp )-H bonds
A solvent-free mixture of alkylbenzene (3 mmol) and Ag/AgBr/TiO
0.003 g) nanotubes as photocatalyst was stirred under CFL White 15
2
(
200 300 400 500 600 700 800 900
wavelength (nm)
W at room temperature in air atmosphere until the reaction was
completed (monitored by TLC). Then the reaction mixture was
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DOI: 10.1039/D0NJ03907A
b)
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Wavelength (nm)
Figure 2. (a) UV–Vis diffuse reflectance spectrum of Ag/AgBr/TiO
nanotubes. (b) photoluminescence emission spectra of TiO (P25)
and Ag /AgBr /TiO nanotubes.
2
2
2
XRD patterns
The XRD patterns are shown in Figure3. Reflections are observed at
◦
◦
◦
◦
◦
2
θ= 25.2 , 37.8 , 48.0 , 54.1 and 62,7 belonging to the (101), (004),
(200), (105) and (204) crystal planes of anatase TiO , respectively.
2
◦
◦
◦
◦
The cubic phase of AgBr appears at 26.64 , 30.91 , 44.29 , 55.01 , and
4.5◦ correspondings to (111), (200), (220), (222), and (400)
crystallographic planes, respectively.31 The crystal size of
Figure 4. a,b) FE-SEM,and c,d) TEM images of Ag/AgBr/TiO
2
6
nanotubes.
Ag/AgBr/TiO
2
is about 15.4 nm, which was determined by Sherrer
FT-IR analysis
˚
equation from 2θ = 30.88 diffraction peak (2θ =30.88˚, λ=0.154178
nm, FWHM= 0.065123).
As shown in Figure 5, the FT-IR spectrum of the Ag/AgBr/TiO
2
nanotubes was recorded. The broad peaks at 400−858 cm-1 are
attributed to the stretching vibration of Ti−O−Ti bonds. Whereas the
absorption peaks at 3426.4 and 1615.2 cm−1 are belonged to the
bending vibration and the stretching vibration of the adsorbed water
FE-SEM and TEM
The FE-SEM images were used to directly analyze the morphology of
the Ag/AgBr/TiO
have nanotube morphology. The pore size (diameter) and length of
the Ag/AgBr/TiO catalyst was estimated at 18.9 nm and 400 nm,
respectively. Moreover, the low and high magnification TEM images
of Ag/AgBr/TiO nanotubes photocatalyst are shown in Figure 4c and
d. As shown in Figure 4d, the approximate size range for the
Ag/AgBr/TiO has measured about 15.60 nm. It should be mentioned
that the estimated average size of the catalyst form TEM images can
be verified by that of the XRD patterns. The TEM images of catalyst
show somewhat that the catalyst morphology is a nanotube.
2
nanotubes (Figure 4a and b). These nanoparticles
−OH group, respectively.
2
2
2
2
Figure 5. FT-IR spectrum of Ag/AgBr/TiO nanotubes.
BET surface area
The data obtained by BET measurements of the synthesized
Ag/AgBr/TiO nanotubes have been given in Table 1. The BET surface
area of Ag/AgBr/TiO was found to be 30.598 m²/g, whereas the BJH
adsorption surface area of pores was 37.797 m²/g. The single point
total pore volume was found to be 0.4193 cm g . The pore diameter
was 54.809 nm.
2
2
3
-1
Figure 3. XRD pattern of the TiO
2 2
, and Ag/AgBr/TiO nanotubes
photocatalyst.
4
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Table 1. Results of BET surface area measurements for
Ag/AgBr/TiO nanotubes.
systems. Therefore, solvent-free conditions wereVieswelAerctitceledOnflioner
performing future experiments. In the next sDteOpI:,1t0h.1e0e3f9f/eDc0tNoJf03907A
2
photocatalyst content was checkout using 0.001-0.02
Ag/AgBr/TiO nanotubes.
g of
BET plot
2
3
-1
V
m
7.03
[cm (STP) g ]
2
-1
a
s,BET
30.59
8
80.43
[m g ]
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7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
C
3
-1
Total pore volume(p/p
0
=0.990)
0.419
3
54.80
9
[cm g ]
Mean pore diameter
[nm]
BJH plot
Adsorption
Plot data
branch
0.4235
3
-1
V
p
[cm g ]
r
p,peak(Area)
45.47
[nm]
2
-1
a
p
37.797
[m g ]
EDX analysis
2
Figure 6. EDX spectrum of Ag/AgBr/TiO nanotubes.
Regarding this Table, the maximum reaction yields achieved in the
presence of 0.003 g of the catalyst (Table 2, entry15). Then, the
photocatalytic reactions were examined under four types of light
(white, blue, green, and red LED) with different waves light (450–750,
450-495, 495-570, and 620-750 nm, respectively). Concerning Table
2, the reaction yield was reached to its maximum value in the
presence of CFL 15 W white. It should be mentioned that the reaction
did not occur in the absence of light (Table 2, entry 23). Moreover, it
must be noted that good yields (65%) were obtained when the
reaction was performed under sunlight (Table 2, entry 24). Also, the
effects of the distinct atmosphere on the conversion of the reactants
were investigated. Similar data were obtained for the oxygen and air
atmosphere (entries 15 and 25), but the argon exhibited much lower
efficiency (entry 26). Hence, the air atmosphere was selected as the
best condition for future reactions. Finally, the photocatalytic activity
The EDX analysis was performed for investigation of the successful
doping of Ag/AgBr in the TiO structure. The results are shown in
Figure 6. As shown in this Figure, the peaks of Ti and O in the EDX are
related to the TiO . Moreover, the corresponding peaks of Ag and Br
are appeared in the EDX, indicating the presence of Ag/AgBr in the
TiO structure.
2
2
2
Following the preparation and characterization of Ag/AgBr/TiO
2
3
nanotubes, to attend access to oxidation of benzylic C(sp )-H bond,
ethylbenzene (1a) for acetophenone (2a) production was chosen as
the model compound. Initially, the effect of the solvent was
investigated. To do this, some polar and nonpolar solvents were
tested. The results are shown in Table 2. According to this Table, the
oxidation reaction of ethylbenzene to its recommended ketone,
acetophenone, in solvent-free condition exhibited a 90% yield (entry
of Ag/AgBr/TiO
2
nanotubes photocatalyst for the oxidation of the
benzylic C(sp )-H bond was comprised of other photocatalysts
(entries 27-30).
1
3).
3
It should be mentioned that the reaction yield in the solvent-free
conditions is comparable or higher than in the solvent-controlled
Table 2. Optimization of the reaction parameters for the procurement of acetophenone a
Amount of
Photocatalyst (g)
Entry
photocatalyst
Solvent
Light
Atmosphere
Conversion (%)
1
2
3
4
5
6
7
8
9
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
2
2
2
2
2
2
2
2
2
2
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
EtOH
CH CN
3
EtOAC
Acetone
THF
MeOH
2
H O
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
air
air
air
air
air
air
air
air
air
air
97
93
95
92
70
90
86
68
64
80
CH
CHCl
DMF
2
Cl
3
2
0.005
0.005
1
0
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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2
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1
1
1
1
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1
1
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Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
Ag/AgBr/TiO
AgBr
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
0.005
0.005
0.005
0.001
0.003
0.007
0.01
DMSO
CN/ H
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
Blue LED 12 W
Green LED 12 W
Red LED 12 W
Dark
air
80
View Article Online
CH
3
2
O
air DOI: 10.1039/D09N2J03907A
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
Solvent Free
air
air
air
air
air
air
air
air
air
air
air
air
balloon
Argon
air
air
air
air
90
90
95
95
95
95
95
84
71
65
0
65
95
30
45
65
50
60
0.015
0.02
0
1
2
3
4
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7
8
9
0
1
2
3
4
5
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19
20
21
0.003
0.003
0.003
0.003
0.003
0.003
0.003
0.003
0.003
0.003
0.003
2
2
2
2
2
2
2
2
3
2
3
4
5
6
7
8
9
0
Sun Light
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
CFL 15 W White
O
2
Ag/AgBr
2
TiO (P25)
Ag/TiO
2
a
Reaction conditions: Ethylbenzene (0.3 mmol), catalyst, 2 mL solvent, at room temperature for 6h.
To show the generality and scope of the oxidation of benzylic C(sp3)- We also failed to synthesize 1- (2-aminophenyl) ethan-1-one, it can
H bond substituted ethylbenzenes and diarylmethanes as the be attributed to the pairing of nitrogen electrons which acts as the
reaction substrate were studied and the results are summarized in hole scavenger, filling the hole and blocking the reaction path (Table
Table 3. Regarding Table 3, ethylene benzene derivatives with 3, entry 2q).
acceptor substitutions have relatively better yields than donor
substitutes.
3
a
Table 3. The scope of photocatalytic oxidative C(sp )-H bonds
O
O
O
O
O
O
N
Cl
2a, 4h, 96%
2b, 42h, 82%
3c, 12h, 41%
2d, 12h, 66%
2e, 12h, 71%
2
f, 12h, 84%
O
O
O
O
O
O
O N
2
F
H CO
H N
Br
3
2
2g, 12h, 92%
2h, 12h, 48%
2i, 12h, 65%
2j,12h, 83%
2k, 12h, 91%
2l, 12h, 86%
O
O
O
O
O
O
HO
B
NH2
HO
N
HO
NO
2m, 12h, 62%
NO2
2n, 12h, 53%
2
2o, 12h, 74%
2p, 12h, 0%
2q, 12h, 0%
2r, 12h, Trace
aReaction conditions: Ethylbenzene and diarylmethane derivatives (0.3 mmol), catalyst (0.003 g) under CFL White 15 W and solvent-free
condition at room temperature in the air atmosphere.
Following the application of Ag/AgBr/TiO
photocatalyst for the oxidation of benzylic C(sp )-H ethylbenzene, details on optimization see SI, Table S2). The selective oxidative
the potential application of the Ag/AgBr/TiO
for the selective aerobic oxidation of C(sp )-H bond of styrene (3a) to the substituted styrenes and the results are summarized in
produce benzaldehyde (4a). The reaction conditions such as Table 4.
photocatalyst quantities, solvents, light sources, atmosphere, as well
as different catalysts were investigated. The best possible reaction
path was achieved when the oxidation was performed under CFL15
2
3
nanotubes as photocatalyst and acetonitrile as the reaction media (for more
2
nanotubes was studied cleavage of the C=C double bond was performed with some of
2
W white irradiation under an air atmosphere at room
temperature using 0.01 g of Ag/AgBr/TiO
2
nanotubes as
6
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/D0NJ03907A
ARTICLE
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
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3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
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1
2
3
4
5
6
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8
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2
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4
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1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Table 4. Scope of benzaldehyde derivatives via oxidation of styrene.
O
O
O
H
O
O
H
H
H
H
H CO
F
Br
3
4a,24h, 90%
from Styrene
4
b,48h, 12%
from (E)-Stilbene
4c,48h, 52%
4d,48h, 42%
4e,48h, 49%
O
O
O
O
O
H
H
H
H
N
and
H
Cl
ClH C
CH Cl
O N
2
2
2
4f,48h, 56%
4g,48h, 88% (mix)
4h,48h, 62%
4i,48h, 54%
O
H
O
H
O
H
H
H
N
O
O
4
j,48h, 57%
4k,48h, 69%
4l,48h, 55%
aReaction conditions: alkene (0.3 mmol), Ag/AgBr/TiO
2
3
nanotubes (0.01g), CH CN (2 mL), irradiation under CFL 15 W white at room
temperature in air atmosphere.
Moreover, the selective oxidation of the C=C bond of α-methyl 65% after 48 h, respectively. Hence, it would be a potential way to
styrene (AMS) as a model reaction for the compounds with an alkyl produce large-scale carbonylation products (Scheme 2). The
substitute at the α-position was investigated (Scheme 1). The result reusability of the Ag/AgBr/TiO
showed that the acetophenone was successfully synthesized via oxidation of benzylic C(sp )-H bond and C(sp )-H bond were also
2
nanotubes photocatalyst for the
3
2
oxidation of α-methyl styrene, indicating of 78 % yield.
examined and the results are summarized in Figure 7a-d. After
completion of the reaction, the catalyst was diluted by ethyl acetate
centrifuged to separate the catalyst dried in an oven and again used
in the next run.
Ag/AgBr/TiO (0.01g)
2
O
CH CN (1 mL)
3
r.t, air, 24h
0
.3 mmol
O
3
m
4 m
10 mmol
8h, 90%
Scheme 1. oxidation of α-methyl styrene (AMS).
O
The optimized reaction condition then was scaled up for the large-
scale synthesis of benzaldehyde and acetophenone. To do this, 10.0
mmol ethylbenzenes in the presence of 0.003 g photocatalyst was
oxidized for the benzaldehyde production, yielded 40% after 4 h and
H
Ag/AgBr/TiO2
10 mmol nanotubes as photocatalyst 48h, 60-65%
Large Scale
9
0% after 8 h, respectively. Also, 10.0 mmol styrene was oxidized in
the presence of 0.01 g of photocatalyst for the synthesis of
acetophenone in large amounts which yielded 45% after 24 h, and
Scheme 2. Schematic representation of large scale synthesis of the
carbonyl compound.
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2
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8
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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
.
-
The photocatalyst was successfully reused with a negligible decrease
in its photocatalytic activity for the oxidation of benzylic C-(sp )-H
bond (six times) and C-(sp )-H bond (four times), indicating the high
2
ability of the Ag/AgBr/TiO nanotubes photocatalyst for recyclable.
It's important to note that after using the photocatalyst several
times, it was found that the intensity of the titanium dioxide peak in
the XRD pattern of the Ag/AgBr/TiO
decreased, although the photocatalyst saves its photocatalytic
activity for the oxidation of both benzylic C(sp )-H and C(sp )-H
bonds.
radical anion O by taking electrons from the conduction band of
2
View Article Online
3
titanium dioxide. The alkylbenzene by givDinOgI:a1n0.1e0le3c9t/rDo0nNJto03t9h0e7A
hole generated a radical cation and followed by intermediate (I)
was produced. The resulted carbocation (I) reacts with peroxide
2
-
anion HOO which was formed from the superoxide radical anion
.
-
O
2
and forms intermediate (II). Finally, the carbonyl bond was
formed.
2
2
nanotubes photocatalyst has
In the case of oxidation of C(sp )-H bonds based on the
information and results obtained from control experiments,
initially, the styrene (1a) is converted to a radical cation by giving
the electron to the hole generated in AgBr. On the other hand, the
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
2
oxygen takes the electron from the conduction band (CB) of TiO
2
.
-
to make superoxide radical anion O
2
. Eventually, the superoxide
and the styrene radical cation react with each
other to form the intermediate III, and subsequently is converted
Suggested mechanisms
.-
radical anion O
2
To clarify the proposed mechanism, we set a series of control
experiments (Scheme 3). By adding a radical scavenger 2,2,6,6 -
tetramethylpiperidine 1-oxyl(TEMPO) to the reaction mixture under
standard conditions, the desired products (acetophenone or
to benzaldehyde.
Conclusions
In summary, Ag/AgBr/TiO ternary component nanotubes as a
heterogeneous photocatalyst were synthesized and characterized
through FT-IR, XRD, FE-SEM, TEM, BET & BJH, UV-Vis. and
2
fluorescence spectroscopy. The Ag/AgBr/TiO
2
nanotubes
photocatalyst was used for the solvent-free oxidation of benzylic
C(sp )-H bond to the corresponding carbonyl compounds or the
3
solvent-controlled selective oxidative cleavage of C=C double
bond of styrene to benzaldehyde under visible light at room
temperature. A wide variety of carbonyl compounds were
successfully synthesized through the developed photocatalytic
process. Moreover, C=C double bond oxidation of α-methyl
styrene as a model reaction for the compounds with an alkyl
substitute at the α-position occurred in good yield. So, our
developed method was shown several advantages such as green
solvent-free oxidation of C-H benzylic, selective oxidation of C=C
double bond of styrene to benzaldehyde, no additional oxidant,
simple and short reaction time and easy separation of product,
promoting the reaction to be green. Moreover, the Ag/AgBr/TiO
2
nanotubes can be used several times without reducing its
photocatalytic activity. According to the reported results,
Ag/AgBr/TiO nanotubes as photocatalyst can be used as an
2
effective and efficient catalyst with high efficiency in a wide range
Figure 7. a) Reusability of the Ag/AgBr/TiO
oxidation of benzylic C(sp )-H bond, b) the corresponding XRD
pattern of the recovered Ag/AgBr/TiO nanotubes photocatalyst,
2
c) Reusability of the photocatalyst in the synthesis of
benzaldehyde derivatives and, d) the corresponding XRD pattern
of the photocatalyst.
2
nanotubes for the
of green reactions.
3
O
TEMPO : Trace
TEA :No Product
standard conditions
+
benzaldehyde) was obtained in a trace amount. We also
investigated the effect of triethanolamine (TEA) as a scavenger to
trap the holes. According to an observation, we found that both
reactions afforded no desired product in the presence of TEA.
These results suggested that the reactions proceeded via the
radical process.
According to the previous reports and based on experimental
results, we proposed the possible mechanism for the synthesis of
carbonyl compounds through the oxidation of the benzylic C(sp )-
Scavenger
O
TEMPO : Trace
TEA :No Product
Scheme 3. Control experiments.
3
2
H and C(sp )-H bonds in Scheme 4. Under the irradiation of visible
light and due to the structural and electronic properties, both Ag
-
and AgBr were photoactive species and generate electron/hole (e
+
/
h ) pairs. The energetic generated electron from plasmon-
excited Ag and CB of AgBr could transfer to the conduction band
7
8,79
(CB) of TiO2.
Oxygen leads to the formation of the superoxide
8
| J. Name., 2012, 00, 1-3
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ARTICLE
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2
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4
5
6
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8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
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3
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6
visible light
1
0. Hosseini-Sarvari, M., Koohgard, M., Firoozi,ViSew.,AMrticolehOajnelirnie,
a
A., and Tavakolian, H, New J. CheDmO.I:, 1200.11083,9/4D20(N9)J,063980870A-
O2
6
888.
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e- e-
11. Jiang, R., Li, B., Fang, C., and Wang, J, Adv. Mater., 2014,
26(31), 5274-5309.
12. Xiong, Z., & Zhao, X. S, J. Am. Chem. Soc., 2012, 134(13),
5754-5757.
e-
OH
R
HOO
R
O2
O
e- e-
O
AgBr
.6 eV
H
Ag
2
Ar
Ar
R
h+
II
TiO2
.2 eV
1
3. An, C., Peng, S., and Sun, Y, Adv. Mater., 2010, 22(23),
Ar
3
h+ h+
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
I
2570-2574.
Ar
R
14. Wang, P., Huang, B., Qin, X., Zhang, X., Dai, Y., Wei, J., and
Whangbo, M. H, Angew. Chem. Int, 2008, 47(41), 7931-
7
933.
1
1
5. Zhou, J., Cheng, Y., & Yu, J, J. Photochem. Photobio. A, 2011,
223(2-3), 82-87.
6. Tejeda, J., Shevchik, N., Braun, W., Goldmann, A., and
b
visible light
O2
O2
Cardona, M, Phys. Rev. B Condens. Matter, 1975, 12(4),
e- e-
O
O
1557.
e-
Ar
O2
e- e-
17. Hu, C., Lan, Y., Qu, J., Hu, X., and Wang, A, Phys. Rev. B
Condens. Matter, 2006, 110(9), 4066-4072.
18. Fan, Y., Ma, W., Han, D., Gan, S., Dong, X., and Niu, L,
Adv. Mater., 2015, 27(25), 3767-3773.
Ag
h+
AgBr
Ar
2.6 eV
O
O
TiO2
.2 eV
e- , H +
Ar
h+ h+
3
O
Ar
Ar
H
19. Zhu, M., Chen, P., and Liu, M, J. Mater. Chem., 2011,
2
1(41), 16413-16419.
2
0. Rycenga, M., Cobley, C. M., Zeng, J., Li, W., Moran, C. H.,
Scheme 4. Proposed mechanism for the synthesis of a) carbonyl
compound b) benzaldehydes catalyzed by Ag/AgBr/TiO nanotubes
photocatalyst under visible light irradiation at room temperature.
Zhang, Q., and Xia, Y, Chem. Rev., 2011, 111(6), 3669-3712.
21. Lin, H., Cao, J., Luo, B., Xu, B., and Chen, S, Catal. Commun.,
012, 21, 91-95.
2. Tian, B., Dong, R., Zhang, J., Bao, S., Yang, F., and Zhang, J,
Appl. Catal., 2014, 158, 76-84.
3. Li, W., Hua, F., Yue, J. and Li, J, Appl. Surf. Sci., 2013, 285,
2
2
2
AUTHOR INFORMATION
2
4
90-497.
Corresponding author, E-mail address: hossaini@shirazu.ac.ir (Mona
Hosseini-Sarvari)
24. Anker, J. N., Hall, W. P., Lyandres, O., Shah, N. C., Zhao, J.,
and Van Duyne, R. P, J. Nanosci. Nanotechno., 2010, 10,
308-319.
5. Zhang, F., Cheng, Z., Cui, L., Duan, T., Anan, A., Zhang, C.,
and Kang, L, RSC Adv., 2016, 6(3), 1844-1850.
6. Long, R., Mao, K., Gong, M., Zhou, S., Hu, J., Zhi, M., and
Zhang, Q, Angew. Chem. Int., 2014, 53(12), 3205-3209.
27. Ye, L., Liu, J., Gong, C., Tian, L., Peng, T., and Zan, L,
2
Acknowledgments
2
The authors gratefully thank the Shiraz University Research Councils
for the support of this work.
ACS Catal., 2012, 2(8), 1677-1683.
2
2
8. Li, H., Gan, S., Wang, H., Han, D., and Niu, L, Adv. Mater.,
015, 27(43), 6906-6913.
9. Hosseini-Sarvari, M., Hosseinpour, Z., and Koohgard, M,
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