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Visible light-induced surface initiated atom transfer radical polymerization of

methyl methacrylate on titania/reduced graphene oxide nanocomposite

Article  in  RSC Advances · February 2015

DOI: 10.1039/C4RA15615C

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Visible light-induced surface initiated atom transfer

radical polymerization of methyl methacrylate on
Cite this: RSC Adv., 2015, 5, 21189
titania/reduced graphene oxide nanocomposite†
Ankushi Bansal,‡a Arvind Kumar,‡a Pawan Kumar,a Sreedhar Bojja,b
Alok K. Chatterjee,a Siddharth S. Ray*a and Suman L. Jain*a

Received 2nd December 2014
Accepted 13th February 2015
DOI: 10.1039/c4ra15615c
www.rsc.org/advances
A novel visible light assisted photoredox catalyst system for surface initiated atom transfer radical
polymerization (SI-ATRP) is developed for polymer growth on the surface of titania/reduced graphene
oxide (TiO2/rGO) nanocomposites using tetrasulfonated copper(II) phthalocyanine (CuPcS) as
catalyst at ambient temperature. The synthesized composite was initially treated with
3-aminopropyltrimethoxysilane (APTMS), and then functionalized with 2-bromoisobutyryl bromide (BIBB)
moieties, serving as a surface initiator for ATRP. In the present method, TiO2/rGO acted as a photoactive
material to reduce Cu(II) to a Cu(I) complex under visible light by a one-electron transfer process as well
as a surface for ATRP initiator immobilization and gave polymer linked TiO2/rGO composites. These
hybrid materials were found to show high dispersability in organic solvents.

The development of visible light assisted polymerization has
received considerable interest and has been extensively used as
a key technique in various applications, such as coatings,
adhesives, medicine, optics and microelectronics.1 The most
oenly used light-induced polymerization methods include
nitroxide-mediated radical polymerization (NMRP),2–4 atom
transfer radical polymerization (ATRP),5 cobalt-mediated
radical polymerization (CMRP)6 and reversible addition–frag-
mentation chain transfer polymerization (RAFT),7–10 etc. Among
the known methods, ATRP11–16 has been considered to be
promising approach mainly due to the wide range of monomers
as well as mild polymerization conditions.17,18 A number of
methods using copper catalysts under various radiation sources
including UV and visible light photoinitiators have been
reported for the light-induced ATRP.19–29 However scanty reports
are known on the light induced surface initiated ATRP. In this
context, Liu et al.30 reported surface-initiated atom transfer
radical polymerization (SI-ATRP) of styrene from initiator
immobilized on silica nanoparticles under UV irradiation. Yan
et al.31 reported ultraviolet light-induced surface-initiated atom-
transfer radical polymerization. This method reported the use
of TiO2 nanoparticles as photoactive materials to reduce Cu(II)/L
a
Chemical Sciences Division, CSIR-Indian Institute of Petroleum, Dehradun-248005,
India. E-mail: suman@iip.res.in; ssray@iip.res.in; Fax: +91-135-2660202; Tel: +91-
135-2525788
b
Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical
Technology, Hyderabad, India
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c4ra15615c
‡ These authors are contributed equally.
to a Cu(I)/L complex under UV irradiation by a one-electron
transfer process for ATRP with multiple usage of monomer
solutions. However, to the best of our knowledge there is no
literature report on the surface initiated light-induced ATRP
under visible light irradiation.
Titanium oxide (TiO2) although has been extensively studied
as a fascinating photocatalyst, but the photocatalytic activity of
TiO2 is limited by the fast electron–hole pair recombination.
When combining TiO2 with graphene, at the interface electrons
will ow from TiO2 to graphene owing to the energy level
structure of the two materials. The heterojunction formed at the
interface (named Schottky barrier) then separates the photo-
excited electron–hole pairs, thus hinders the charge recombi-
nation and enhance their photocatalytic activities.32 The
enhancement of photocatalytic activity of graphene-based
semiconductor–metal composites was rst demonstrated by
Kamat and co-workers in 2010.33 Later on, a number of studies
for various applications including photocatalytic degradation of
organic pollutants, photocatalytic reduction and other catalytic
reactions have been reported.34,35
Herein we report the rst successful visible light assisted
surface initiated ATRP of methyl methacrylate (MMA) on the
surface of TiO2/rGO composite at ambient temperature. For this
purpose, we have used tetrasulfonated copper(II) phthalocyanine
(CuPcS) as a catalyst which is being reduced to Cu(I) complex
under visible light irradiation by a one-electron transfer process
for ATRP and the initiator used was self-assembled on the
surface of the TiO2/rGO to give surface bound initiators
(Br@TiO2/rGO). Thus TiO2/rGO is playing dual role i.e. photo-
catalyst as well as surface for ATRP initiator immobilization.

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Results and discussion
Synthesis and characterization of Br@TiO2/rGO and
PMMA@TiO2/rGO composites
The synthesis strategy that has been employed is shown in
Scheme 1. Composite material of rGO and TiO2 was obtained
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via in situ hydrothermal synthesis using graphene oxide (GO)
and titanium isopropoxide(IV) as starting materials. During the
reaction, deoxygenation of GO and deposition of TiO2 nano-
structures on GO surface occurs simultaneously, yielding the
uniform composites with strong physical and chemical
binding. The weight percentage of the components in the
synthesized TiO2/rGO composite was determined by elemental
analysis for carbon and ICP-AES analysis for titanium. The
titanium and carbon elemental analysis showed that the
materials are composed of approximately 40.2 wt% of TiO2 and
ca. 50 wt% carbon in the synthesized TiO2/rGO composite. The
synthesized composite material was well characterized with
various techniques including X-ray diffraction (XRD), FT-IR,
scanning electron microscopy (SEM), high-resolution trans-
mission electron microscopy (HR-TEM), and thermal gravi-
metric analysis/differential thermal analysis (TGA/DTA). The
amino functionalization of the synthesized TiO2/rGO compos-
ites was carried out by using 3-aminopropyltrimethoxysilane
(APTMS) as a coupler. The amino functionalized TiO2/rGO
nanocomposite was subsequently treated with excess of 2-bro-
moisobutyryl bromide (BIBB) in the presence of triethylamine
(TEA) and dichloromethane (DCM) in an ice bath for 24 h. SEM
images of NH2–TiO2/rGO and Br@NH2–TiO2/rGO are shown in
the ESI (Fig. S1 and S2†). Elemental mapping of NH2–TiO2/rGO
(Fig. S1d†) and Br@NH2–TiO2/rGO (Fig. S2d†) clearly indicates
the uniform distribution of nitrogen (green dots) and bromine
(yellow dots) on the surface of TiO2/rGO. Aer collecting the
material via ltration, the obtained Br@NH2–TiO2/rGO was then
vigorously washed with chloroform and deionized water to
remove residual reactants. Finally the initiator functionalized
nanocomposites were used for the graing of polymer chains
using MMA via SI-ATRP technique under visible light (Scheme 1).
The FT-IR spectrum of TiO2/rGO (Fig. 1a) shows vibrational
bands at ca. 3410 cm
1 due to hydroxyl group stretching
vibrations in COOH and/or intercalated water. It was observed
that the peaks due to oxygen-containing functionalities in gra-
phene oxide (GO) such as C–O and C–OH which were usually
Scheme 1 Schematic representation of the visible light-assisted
surface initiated ATRP of MMA on TiO2/rGO support.
21190 | RSC Adv., 2015, 5, 21189–21196
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appeared at 1058 cm
1 and 1227 cm
1 respectively, were
dramatically reduced for TiO2/rGO composite. The strong band
at 1630 cm
1 is corresponding to the aromatic C]C presented
in the rGO. The appearance of strong absorption bands at 450
and 670 cm
1, indicating the presence of Ti–O–Ti bond in
TiO2/rGO. Aer the graing of NH2 functionalities on the
surface of TiO2/rGO composite, the IR spectrum shows a
doublet at around 2926 and 2973 cm
1 corresponds to
symmetric and asymmetric vibrations of CH2 of the alkyl chains
assigning to silane moieties of APTMS conrmed the successful
graing of amino silane moieties on the TiO2/rGO support.
Moreover, the appearance of bands at 1620 cm
1 corresponding
to primary NH, 1108 cm
1, 1037 cm
1 and 1597 cm
1 due to
Si–O–Si, Si–O–C and C]C vibration, respectively provided more
evidence for the successful chemical functionalization. In the
FT-IR of Br@NH2–TiO2/rGO, the characteristic absorption band of
amide group (CONH) appeared at 1641 cm
1 along with peaks at
1456 cm
1 and 1379 cm
1 which are assigned to the C–H bending
vibration of the methyl groups of the initiator. This conrmed the
successful graing of the ATRP initiator on the TiO2/rGO surface.
The FTIR spectra of PMMA@Br@NH2–TiO2/rGO (Fig. 1d)
exhibits a new absorbance band at 1732 cm
1 attributed to the
ester groups of PMMA. Other PMMA peaks due to the –C–O (ester)
linkage appeared in the range of 1200–1000 cm
1. However, the
stretching and bending vibration of aliphatic C–H were appeared
in the region of 2846–2997 cm
1 and 950–650 cm
1 respectively.
The XRD patterns of the TiO2/rGO composite (Fig. 2b) shows
characteristic peaks at 2q values of 25.3 , 37.8 , 48.1 , 53.9 and
55.1 which can be indexed to the (101), (004), (200), (105) and
(211) crystal planes of a tetragonal anatase JCPDS no. 21-1272
with lattice constants a ¼ 3.78 Å and c ¼ 9.50 Å. This indicates
Fig. 1 FT-IR of the synthesized nanocomposites (a) TiO2/rGO; (b)
NH2–TiO2/rGO; (c) Br@NH2–TiO2/rGO; (d) PMMA@Br@NH2–TiO2/rGO.
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that the in situ synthesis of TiO2 nanoparticles on the rGO

surface via hydrothermal method converts the amorphous TiO2
into anatase TiO2. Furthermore, disappearance of characteristic
diffraction peak of graphene oxide (Fig. 2a) indicates that
exfoliation of the layered GO and formation of TiO2/rGO
composite was obtained (Fig. 2b). In the XRD patterns of
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PMMA@TiO2/rGO, some amorphous pattern of polymer is

observed nearly at 2q (18 ) indicating that the polymerization
is occurred at the surface of TiO2/rGO composite (Fig. 2c).
The morphology of the synthesized TiO2/rGO composites
was determined by SEM and TEM analyses as shown in
Fig. 3a–f. The SEM image of graphene oxide showed crumpled
structure with folded sheets (Fig. 3a). The SEM images of
hydrothermally synthesized TiO2/rGO composites revealed that Fig. 3 SEM images of (a) GO; (b) TiO2/rGO; (c) EDX of TiO2/rGO; TEM
images of (d) GO; (e) TiO2/rGO; (f) SAED pattern of TiO2/rGO
TiO2 nanoparticles were embedded in reduced graphene oxide
composite.
hybrid structure (Fig. 3b). EDX pattern further conrmed the
presence of TiO2 in nanocomposite (Fig. 3c). TEM image of
graphene oxide exhibited transparent single layered folded
remaining oxygen functionalities of rGO. Further it indicates
sheets as shown in Fig. 3d. As depicted in Fig. 3e, these sheets of
that TiO2/rGO exhibit better thermal stability due to the strong
graphene oxide aer the hydrothermal treatment was wrapped
interaction of TiO2 with rGO sheets by hydrothermal treatment
on TiO2. SAED pattern of TiO2/rGO composite showed the
at 180  C for 24 h. The amino functionalized (NH2–TiO2/rGO)
diffraction pattern of crystalline TiO2 along with one to two
nanocomposites exhibited major weight loss in the range of
rings due to amorphous rGO (Fig. 3f). The number of rings in
200–450  C, which is most likely due to the decomposition of
SAED pattern also conrmed that sheets were single or double
organosilane moieties presented on the surface. Furthermore,
layered. As presented in Fig. S3a (ESI†), the SEM image of
the more weight loss observed in Br@NH2–TiO2/rGO is due to
polymer functionalized TiO2/rGO showed that the functional-
the decomposition of ATRP initiator molecules immobilized to
ized platelets became wrinkled and folded during the poly-
the surface of functionalized TiO2/rGO composites. Aer the
merization process at surface. However, from TEM image
decomposition of the thermally labile oxygen functionalities
(Fig. S3b†) it is clear that the polymer chains covered the surface
and initiator groups, there was no considerable mass loss upto
of the platelets and TiO2/rGO was exfoliated to single layers.
800  C (Fig. 4).
Fig. 4 displayed the thermal decomposition behaviour of the
The chemical composition of the composites at various stages
synthesized composites i.e. TiO2/rGO, NH2–TiO2/rGO and
of surface modication was determined by XPS. Fig. 5a shows
Br@NH2–TiO2/rGO at different temperatures, respectively. The
the representative XPS wide scan spectra of the Br@NH2–TiO2/
weight loss of TiO2/rGO (Fig. 4a) was about 8.5% (Table 1) when
rGO. It exhibits distinct peaks of C (286 eV, C 1s), N (403 eV, N ls),
heated from room temperature to 900  C and is believed to be
O (534 eV, O 1s), Ti (460 eV, Ti 2p), Si 2s, Si 2p, Br 3p and Br 3d.
due to the evaporation of absorbed water molecules and
The appearance of a strong Br 3d and Br 3p signals at the binding

Fig. 2 XRD pattern of (a) GO; (b) TiO2/rGO; (c) PMMA@TiO2/rGO. Fig. 4 TGA of TiO2/rGO, NH2–TiO2/rGO and Br@NH2–TiO2/rGO.

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Table 1 Thermal degradation parameters of PMMA@TiO2/rGO at then dried under vacuum. The TiO2/rGO composite materials
various polymerization times ranging from 5 to 24 h as obtained from containing poly methylmethacrylate (PMMA) at the surface were
TGA
examined by thermo-gravimetric analysis (TGA) to obtain the
Decomposition gra content of PMMA to TiO2/rGO surface quantitatively. The
Sample Weight loss (%) temp ( C) thermal decomposition behaviour of PMMA@TiO2/rGO at
various polymerization times ranging from 5 h to 24 h is shown
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TiO2/rGO 8.5 92 in Fig. 6.

NH2–TiO2/rGO 14.2 395
Br@NH2–TiO2/rGO 21.1 228
It is indeed clear that the thermal decomposition prole of
Graed PMMA (5 h) 58.5 561 these polymer functionalized composites is rather different
Graed PMMA (10 h) 73.4 383 from those of TiO2/rGO and TiO2/rGO composites. The major
Graed PMMA (20 h) 96 374 weight loss in these polymer graed nanocomposites was
Graed PMMA (24 h) 98.9 371 occurred at 370–380  C, which is mainly attributed to the
Free PMMA 100 365
decomposition of the polymer chains graed to the function-
alized TiO2/rGO nanocomposites. The content of the polymer
shell as calculated from the TGA data was found to be in the
energies of about 71 and 189 eV (Fig. 5b and c), respectively are in range from 21 to 98.9% as shown in Table 1. The decomposition
good agreement with the existing literature reports.36 temperature of the PMMA moieties in polymer functionalized
Upon synthesis and characterization of the ATRP initiator- TiO2/rGO was appeared at 370–380  C, which is 5–15  C higher
functionalized TiO2/rGO nanocomposites, subsequent efforts than that of free-PMMA (ca. 365  C), indicating that the thermal
were made towards the photo-assisted growth of polymers on its stability of the PMMA chains can be dramatically improved by
surface in a controlled fashion under visible light irradiation. A linkage with TiO2/rGO.
series of polymerization experiments were performed by adding To characterize the graed polymers, the surface attached
monomer MMA and CuPcS to a DMF mixture containing the PMMA chains were detached from the TiO2/rGO surface via
aforementioned initiator functionalized TiO2/rGO composite. saponication with NaOH in DMF. The number average
The resulting mixtures were irradiated by visible light at room molecular weight (Mn) and molecular weight distribution
temperature for 5–24 h. Aer the reaction, the polymer func- (Mw/Mn) of the detached PMMA samples was determined by gel
tionalized TiO2/rGO samples were washed with excess DMF and permeation chromatography (GPC) analysis. As shown in Fig. 7,
the molecular weights of detached PMMA (d-PMMA) increased
in accordance with the time of polymerization with increased
conversion from 42 to 90% (i.e. 5–24 h respectively). In addition
the Mn of the cleaved PMMA chains increases linearly with
conversion from 20 172 to 25 910 with a relatively low poly-
dispersities decreases from 1.37 to 1.29, respectively with
increasing the conversion. These results suggested that the
aforementioned surface initiated polymerization (SIPs) pro-
ceeded in a controlled manner.

Fig. 5 XPS spectra of Br@NH2–TiO2/rGO (a) wide scan spectra, (b) Br

3p, (c) Br 3d of Br@NH2–TiO2/rGO indicates that initiator moiety was Fig. 6 TGA of polymer grafted surface (PMMA@TiO2/rGO) at different
covalently attached on the surface of amino functionalized TiO2/rGO. polymerization time.

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Fig. 7 GPC chromatogram measured molecular weight (Mn) and
molecular weight distribution (Mw/Mn) of cleaved PMMA with poly-
merization conversion ranged from 42 to 90% in DMF using Br@NH2–
TiO2/rGO as initiator under visible light assisted ATRP.
In order to check the effect of visible light, we performed the
blank polymerization experiment under dark conditions in
absence of visible light. As expected, no polymerization was
obtained even aer prolonged time under otherwise identical
reaction conditions. These results clearly indicated that the
visible light is an essential component for making polymer/
nanocomposite hybrids by this approach.
Further we studied the difference in the graing density by
varying the amount of initiator concentration during the gra-
ing process. Two graing densities (low and high) of the initi-
ator were bonded to the TiO2/rGO surface, and the
concentration of initiator used for the high initiator density was
four times that of the low initiator density. Thermogravimetric
analysis (TGA) was used to assess the control of graing density
and chain length by determining the weight loss at 600  C under
nitrogen atmosphere. TGA results showed, a lower weight loss
(approx. 50 wt%) in case of composite having lower amount of
the loaded initiator. However, the samples having higher
concentration of graed initiator showed higher weight loss
(85 wt%) indicating a difference in graing density.
To explain the visible light activity of the TiO2/rGO nano-
composite we have calculated the optical band gap by Tauc's
plot Fig. 8. The band gap value for TiO2 was found to be 3.2 eV
Fig. 8 Tauc plot of TiO2 and TiO2/rGO.
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Scheme 2 Possible mechanism of visible light induced SI-ATRP on
TiO2/rGO.
associated with 387 nm (UV) that was in well conformity with
literature value.32 It is clear that this band gap was high enough
to prevent any visible light mediated transition. While for the
TiO2/rGO nanocomposite two band gap values at 3.2 eV and
2.4 eV (515 nm) was found. The band gap at 3.2 was observed
due to individual transition of TiO2 while the band gap at 2.4 eV
was observed due to synergistic effect of TiO2/rGO nano-
composite and clearly depicted that the composite was visible
light active.
On the basis of band gap values, we have explained a plausible
mechanism for the polymerization of MMA on the surface of
TiO2/rGO under visible light using Cu(II)PcS as a catalyst and DMF
as solvent is illustrated in Scheme 2. As shown, the absorption of
visible light by TiO2/rGO composite generates positive holes (h+)
and electrons (e
), in the conduction and valence bands of TiO2.
Reduced graphene oxide due to their specic nature of higher
electron mobility prevent the recombination of photo-generated
electron–hole pairs.32 These photogenerated electrons were used
for in situ reduction of Cu(II)PcS to Cu(I)PcS, which acted as an
activator in the ATRP. Thus generated Cu(I)PcS promote the
homolysis of C–Br bond of Br@NH2–TiO2/rGO initiator
and produces alkyl radicals which subsequently leads the living
polymerization of MMA (Scheme 2).
In summary, we have demonstrated rst successful visible
light assisted surface-initiated atom transfer radical polymeri-
zation of MMA on initiator modied TiO2/rGO nanocomposites
using tetrasulfonated copper(II) phthalocyanine as catalyst. In
the developed methodology, the TiO2/rGO acted as a photo-
active material which involves the generation of a positive hole
(h+) and an electron (e
) in conduction and valence bands of
TiO2, respectively. The valence band electron is subsequently
used to reduce Cu(II) to a Cu(I) complex under visible light by a
one-electron transfer process. The in situ generated Cu(I)PcS
acted as an activator in the SI-ATRP. Subsequently, the poly-
merization of MMA was started by the activation of polymeri-
zation initiator by the Cu(I)PcS at surface for ATRP to give the
TiO2/rGO based nanoparticles hybrids linking PMMA segments.
Experimental section
Materials
The monomer, MMA (>99%), was purchased from Sigma-
Aldrich. It was washed three times with an aqueous solution of
RSC Adv., 2015, 5, 21189–21196 | 21193

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sodium hydroxide (5 wt%), followed by deionized water until
neutralization and then dried over anhydrous magnesium
sulfate, distilled under reduced pressure, and stored at
18  C
for further use. Graphite akes, titanium isopropoxide(IV) (97%),
(3-aminopropyl)trimethoxysilane (APTMS, 99%), 2-bromoisobu-
tyryl bromide (BIBB, 98%) and triethylamine (TEA, 99%) was
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purchased from Sigma-Aldrich and were used as received.
Potassium permanganate 99.0%, sodium nitrate 99.0%,
concentrated sulfuric acid, hydrogen peroxide (30%), hydro-
chloric acid, acetic acid, 2-butanol, ethanol, dichloromethane
(DCM), dimethylformamide (DMF), tetrahydrofuran (THF) were
purchased from Merck (India). All chemicals and solvents were
of analytical grade and used as received. Tetrasulfonated copper
phthalocyanine (CuPcS) was synthesized according to reported
literature method with little modication.37
Characterization techniques
Fourier Transform Infrared Spectroscopy (FT-IR) was conducted
by Perkin-Elmer Spectrum RX-1 IR spectrophotometer. High
resolution transmission electron microscopy (HR-TEM) of the
samples was executed using a JEOL JEM 2100 Microscope.
Scanning electron microscopy (SEM) was performed by Jeol
Model JSM-6340F. For FE-SEM analysis aqueous dispersions of
GO, TiO2/rGO and functionalized TiO2/rGO samples were
deposited on the glass slides, while very dilute aqueous
suspensions were deposited on carbon coated copper grids for
HR-TEM analysis. X-ray powder diffraction (XRD) analyses were
carried out using a Bruker D8 Advance diffractometer at 40 kV
and 40 mA with Cu Ka radiation (l ¼ 0.15418 nm). Sample for
XRD was prepared by the deposition of well dispersed func-
tionalized graphene–TiO2 samples on glass slide followed by
drying; the analysis was performed by using cobalt as the target
material. Thermo gravimetric analyses (TGA) of these samples
were carried out using a thermal analyzer TA-SDT Q-600. All
samples were analyzed in the temperature range of 40 to 800  C
at a heating rate of 10  C min
1 under the nitrogen ow.
Molecular weight and molecular weight distribution were
measured by using Agilent HPLC/GPC system comprising of
1200 innity series precision Pump, 1200 Series Diode Array
detector & 1260 innity Evaporative Light Scattering Detector.
XPS measurements were obtained on a KRATOS-AXIS
165 instrument equipped with dual aluminum–magnesium
anodes by using Mg-Ka radiation (hn ¼ 1253.6 eV) operated at
5 kV and 15 mA with pass energy 80 eV and an increment of
0.1 eV. To overcome the charging problem, a charge neutralizer
of 2 eV was applied and the binding energy of C 1s core level
(BE z 4.6 eV) of adventitious hydrocarbon was used as a stan-
dard. The XPS spectra were tted by using a nonlinear square
method with the convolution of Lorentzian and Gaussian
functions, aer a polynomial background was subtracted from
the raw spectra. ICP-AES analysis was carried out by inductively
coupled plasma atomic emission spectrometer (ICP-AES, DRE,
PS-3000UV, Leeman Labs Inc., USA). Samples for ICP-AES were
prepared by leaching out 0.01 g of sample with HNO3 (conc.),
and then heated for 30 min and volume to 10 mL. The elemental
analysis has been carried out using Elementar vario micro cube
21194 | RSC Adv., 2015, 5, 21189–21196
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unit. Photoirradiation was carried out under visible light by
using 20 W white cold LED ood light (model no. HP-FL-20W-F-
Hope LED Opto-Electric Co., Ltd.). Intensity of the light at vessel
was measured by intensity meter and was found to be 75 W m
2.
Preparation of graphene oxide (GO)
Graphene oxide was prepared from graphite akes using
modied Hummers methods.38 In a typical synthesis, concen-
trated H2SO4 (34 mL) was added into a ask containing graphite
akes (1 g) and sodium nitrate (0.75 g) under stirring at 0  C
(ice bath). Then approximately 4.5 g of KMnO4 was added gently
to the mixture over 20 min and kept under stirring at room
temperature for ve days. Aer that 50 mL diluted H2SO4
(5 wt%) was added into the mixture and heated upto 90  C
under continuous stirring for 2 h. Then 30 wt% H2O2 solution
(2.7 mL) was added into the solution and stirred for another 2 h
under ambient conditions. Aer completion of the reaction, the
mixture was centrifuged (6000 rpm, 15 min) and washed with
H2SO4 (3 wt%), H2O2 (0.5 wt%), and HCl (3 wt%), and then
repeatedly washed with distilled water until the pH of the
ltrate became neutral. Finally, the prepared GO was dispersed
in distilled water and the homogeneous GO dispersion was then
centrifuged and ltered.
Synthesis of TiO2/rGO composites by in situ hydrothermal
method
In a typical synthesis, graphene oxide (40 mg) was dispersed in
distilled water (60 mL) by sonication for 30 min. Titanium iso-
propoxide(IV) (20 mmol) in 20 mL acetic acid and 5 mL 2-butanol
was added into the ask containing dispersed GO. The resulting
mixture was vigorously stirred at 60  C for 5 h. Aer the reaction,
the obtained mixture was hydrothermally treated in a autoclave at
180  C for 24 h. Then, the product was separated by centrifuga-
tion and washed with water for 3–4 times. Finally the obtained
solid was washed with ethanol and dried under vacuum.
Synthesis of NH2-functionalized TiO2/rGO nanocomposite
(NH2–TiO2/rGO)
Typically, 0.25 g of TiO2/rGO, 50 mL of freshly distilled ethanol,
and 2.5 mL of APTMS (0.011 mol) were placed in a 100 mL ask.
Aer evacuating air with N2 for 20 min, the ask was immersed
in an oil bath at 65  C. The mixture was stirred for 24 h under
nitrogen atmosphere, then the solution was cooled and washed
with abundant toluene and acetone in ultrasonic and collected
product was dried under vacuum at room temperature for 24 h.
Synthesis of ATRP initiator immobilized composites
(Br@NH2–TiO2/rGO)
0.25 g of amino-functionalized rGO/TiO2 (NH2–TiO2/rGO) and
40 mL of DCM were loaded in a dried 100 mL round bottom
ask and sonicated for 30 min to prepare a colloidal suspension
of NH2@TiO2/rGO. Then 2 mL (0.014 mol) of triethylamine were
added in a round bottom ask and immersed in an ice water
bath. The solution was stirred followed by addition of 2-bro-
moisobutyryl bromide (0.012 mol) drop wise into the mixture.
This journal is © The Royal Society of Chemistry 2015

Paper
Thereaer, the initiator functionalized NH2–TiO2/rGO (herein-
aer refer to Br@NH2–TiO2/rGO) were thoroughly washed in
dichloromethane and ethanol ultrasonically to remove residual
reactants and by-product and dried under vacuum at room
temperature for 24 h.
Published on 13 February 2015. Downloaded by Indian Institute of Technology New Delhi on 27/02/2015 16:06:16.
General procedure for surface-initiated ATRP of MMA under
visible light irradiation
In this typical polymerization experiment, 0.02 g Br@NH2–TiO2/
rGO, 0.027 g of Cu(II)PcS, MMA (0.018 mol) and DMF (2 mL;
monomer/solvent ¼ 1 : 1 v/v) was added into a dried borosil
round bottom ask equipped with magnetic bar under stirring
to give a well-dispersed solution. Aer sealing with a rubber
septum, the ask was evacuated and then purged with nitrogen
(3 cycles) to remove oxygen. Then sealed and evacuated ask
was placed in front of LED (visible light source) to carry out
visible light induced surface initiated ATRP at room tempera-
ture. Aer the desired polymerization time, the reaction mixture
was put in ice cold bath and diluted by THF and polymer was
precipitated by adding excess of cold methanol.
Saponication of polymer chains from the surfaces of poly-
mer functionalized TiO2/rGO composites. Sodium hydroxide
(300 mg) was mixed with a solution of PMMA@TiO2/rGO in
DMF (5 mL of DMF) and the resulting mixture was stirred at
80  C for 7 days. The opaque solution was then ltered through
a Whatman 2.0 mm polycarbonate membrane lter. The ltrate
was added into excess methanol for the precipitation. The
precipitated solid was then washed with methanol and deion-
ized water (2  50 mL) to remove residual base. The resulting
material was then vacuum-dried, dissolved in THF and sub-
jected to GPC analysis.
Acknowledgements
We kindly acknowledge Director, CSIR-IIP for his permission to
publish these results. A. Bansal acknowledges CSIR, New Delhi
for providing the nancial support in terms of research fellow-
ship. Raghuvir Singh and G. M. Bahuguna, C. D. Sharma, San-
deep Saran, K. L. N. Siva Kumar are acknowledged for providing
spectra for FTIR, XRD, TGA, GPC and SEM respectively.
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