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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)
Received 2nd December 2014
Accepted 13th February 2015
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
DOI: 10.1039/c4ra15615c
as a surface for ATRP initiator immobilization and gave polymer linked TiO2/rGO composites. These
www.rsc.org/advances hybrid materials were found to show high dispersability in organic solvents.
The development of visible light assisted polymerization has to a Cu(I)/L complex under UV irradiation by a one-electron
received considerable interest and has been extensively used as transfer process for ATRP with multiple usage of monomer
a key technique in various applications, such as coatings, solutions. However, to the best of our knowledge there is no
adhesives, medicine, optics and microelectronics.1 The most literature report on the surface initiated light-induced ATRP
oenly used light-induced polymerization methods include under visible light irradiation.
nitroxide-mediated radical polymerization (NMRP),2–4 atom Titanium oxide (TiO2) although has been extensively studied
transfer radical polymerization (ATRP),5 cobalt-mediated as a fascinating photocatalyst, but the photocatalytic activity of
radical polymerization (CMRP)6 and reversible addition–frag- TiO2 is limited by the fast electron–hole pair recombination.
mentation chain transfer polymerization (RAFT),7–10 etc. Among When combining TiO2 with graphene, at the interface electrons
the known methods, ATRP11–16 has been considered to be will ow from TiO2 to graphene owing to the energy level
promising approach mainly due to the wide range of monomers structure of the two materials. The heterojunction formed at the
as well as mild polymerization conditions.17,18 A number of interface (named Schottky barrier) then separates the photo-
methods using copper catalysts under various radiation sources excited electron–hole pairs, thus hinders the charge recombi-
including UV and visible light photoinitiators have been nation and enhance their photocatalytic activities.32 The
reported for the light-induced ATRP.19–29 However scanty reports enhancement of photocatalytic activity of graphene-based
are known on the light induced surface initiated ATRP. In this semiconductor–metal composites was rst demonstrated by
context, Liu et al.30 reported surface-initiated atom transfer Kamat and co-workers in 2010.33 Later on, a number of studies
radical polymerization (SI-ATRP) of styrene from initiator for various applications including photocatalytic degradation of
immobilized on silica nanoparticles under UV irradiation. Yan organic pollutants, photocatalytic reduction and other catalytic
et al.31 reported ultraviolet light-induced surface-initiated atom- reactions have been reported.34,35
transfer radical polymerization. This method reported the use Herein we report the rst successful visible light assisted
of TiO2 nanoparticles as photoactive materials to reduce Cu(II)/L 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
a
Chemical Sciences Division, CSIR-Indian Institute of Petroleum, Dehradun-248005, (CuPcS) as a catalyst which is being reduced to Cu(I) complex
India. E-mail: suman@iip.res.in; ssray@iip.res.in; Fax: +91-135-2660202; Tel: +91-
under visible light irradiation by a one-electron transfer process
135-2525788
b
for ATRP and the initiator used was self-assembled on the
Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical
Technology, Hyderabad, India surface of the TiO2/rGO to give surface bound initiators
† Electronic supplementary information (ESI) available. See DOI: (Br@TiO2/rGO). Thus TiO2/rGO is playing dual role i.e. photo-
10.1039/c4ra15615c catalyst as well as surface for ATRP initiator immobilization.
‡ These authors are contributed equally.
This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 21189–21196 | 21189
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Results and discussion appeared at 1058 cm1 and 1227 cm1 respectively, were
dramatically reduced for TiO2/rGO composite. The strong band
Synthesis and characterization of Br@TiO2/rGO and at 1630 cm1 is corresponding to the aromatic C]C presented
PMMA@TiO2/rGO composites in the rGO. The appearance of strong absorption bands at 450
The synthesis strategy that has been employed is shown in and 670 cm1, indicating the presence of Ti–O–Ti bond in
Scheme 1. Composite material of rGO and TiO2 was obtained TiO2/rGO. Aer the graing of NH2 functionalities on the
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via in situ hydrothermal synthesis using graphene oxide (GO) surface of TiO2/rGO composite, the IR spectrum shows a
and titanium isopropoxide(IV) as starting materials. During the doublet at around 2926 and 2973 cm1 corresponds to
reaction, deoxygenation of GO and deposition of TiO2 nano- symmetric and asymmetric vibrations of CH2 of the alkyl chains
structures on GO surface occurs simultaneously, yielding the assigning to silane moieties of APTMS conrmed the successful
uniform composites with strong physical and chemical graing of amino silane moieties on the TiO2/rGO support.
binding. The weight percentage of the components in the Moreover, the appearance of bands at 1620 cm1 corresponding
synthesized TiO2/rGO composite was determined by elemental to primary NH, 1108 cm1, 1037 cm1 and 1597 cm1 due to
analysis for carbon and ICP-AES analysis for titanium. The Si–O–Si, Si–O–C and C]C vibration, respectively provided more
titanium and carbon elemental analysis showed that the evidence for the successful chemical functionalization. In the
materials are composed of approximately 40.2 wt% of TiO2 and FT-IR of Br@NH2–TiO2/rGO, the characteristic absorption band of
ca. 50 wt% carbon in the synthesized TiO2/rGO composite. The amide group (CONH) appeared at 1641 cm1 along with peaks at
synthesized composite material was well characterized with 1456 cm1 and 1379 cm1 which are assigned to the C–H bending
various techniques including X-ray diffraction (XRD), FT-IR, vibration of the methyl groups of the initiator. This conrmed the
scanning electron microscopy (SEM), high-resolution trans- successful graing of the ATRP initiator on the TiO2/rGO surface.
mission electron microscopy (HR-TEM), and thermal gravi- The FTIR spectra of PMMA@Br@NH2–TiO2/rGO (Fig. 1d)
metric analysis/differential thermal analysis (TGA/DTA). The exhibits a new absorbance band at 1732 cm1 attributed to the
amino functionalization of the synthesized TiO2/rGO compos- ester groups of PMMA. Other PMMA peaks due to the –C–O (ester)
ites was carried out by using 3-aminopropyltrimethoxysilane linkage appeared in the range of 1200–1000 cm1. However, the
(APTMS) as a coupler. The amino functionalized TiO2/rGO stretching and bending vibration of aliphatic C–H were appeared
nanocomposite was subsequently treated with excess of 2-bro- in the region of 2846–2997 cm1 and 950–650 cm1 respectively.
moisobutyryl bromide (BIBB) in the presence of triethylamine The XRD patterns of the TiO2/rGO composite (Fig. 2b) shows
(TEA) and dichloromethane (DCM) in an ice bath for 24 h. SEM characteristic peaks at 2q values of 25.3 , 37.8 , 48.1 , 53.9 and
images of NH2–TiO2/rGO and Br@NH2–TiO2/rGO are shown in 55.1 which can be indexed to the (101), (004), (200), (105) and
the ESI (Fig. S1 and S2†). Elemental mapping of NH2–TiO2/rGO (211) crystal planes of a tetragonal anatase JCPDS no. 21-1272
(Fig. S1d†) and Br@NH2–TiO2/rGO (Fig. S2d†) clearly indicates with lattice constants a ¼ 3.78 Å and c ¼ 9.50 Å. This indicates
the uniform distribution of nitrogen (green dots) and bromine
(yellow dots) on the surface of TiO2/rGO. Aer 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 graing 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 cm1 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 Fig. 1 FT-IR of the synthesized nanocomposites (a) TiO2/rGO; (b)
surface initiated ATRP of MMA on TiO2/rGO support. NH2–TiO2/rGO; (c) Br@NH2–TiO2/rGO; (d) PMMA@Br@NH2–TiO2/rGO.
21190 | RSC Adv., 2015, 5, 21189–21196 This journal is © The Royal Society of Chemistry 2015
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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.
This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 21189–21196 | 21191
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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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21192 | RSC Adv., 2015, 5, 21189–21196 This journal is © The Royal Society of Chemistry 2015
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Experimental section
Materials
The monomer, MMA (>99%), was purchased from Sigma-
Fig. 8 Tauc plot of TiO2 and TiO2/rGO. Aldrich. It was washed three times with an aqueous solution of
This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 21189–21196 | 21193
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sodium hydroxide (5 wt%), followed by deionized water until unit. Photoirradiation was carried out under visible light by
neutralization and then dried over anhydrous magnesium using 20 W white cold LED ood light (model no. HP-FL-20W-F-
sulfate, distilled under reduced pressure, and stored at 18 C Hope LED Opto-Electric Co., Ltd.). Intensity of the light at vessel
for further use. Graphite akes, titanium isopropoxide(IV) (97%), was measured by intensity meter and was found to be 75 W m2.
(3-aminopropyl)trimethoxysilane (APTMS, 99%), 2-bromoisobu-
tyryl bromide (BIBB, 98%) and triethylamine (TEA, 99%) was
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21194 | RSC Adv., 2015, 5, 21189–21196 This journal is © The Royal Society of Chemistry 2015
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Thereaer, the initiator functionalized NH2–TiO2/rGO (herein- 8 S. Muthukrishnan, E. H. Pan, M. H. Stenzel, C. Barner-
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17 K. Matyjaszewski and J. Xia, Chem. Rev., 2001, 101, 2921–
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18 L. Ren, S. Huang, C. Zhang, R. Wang, W. W. Tjiu and T. Liu,
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19 M. A. Tasdelen, M. Cici and Y. Yagci, Macromol. Chem.
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21 M. Tanabe, W. M. V. Guido, W. Y. Chan, P. W. Cyr,
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Acknowledgements 23 D. Konkolewicz, K. Schröder, J. Buback, S. Bernhard and
K. Matyjaszewski, ACS Macro Lett., 2012, 1, 1219–1223.
We kindly acknowledge Director, CSIR-IIP for his permission to 24 E. H. H. Wong, S. N. Guntari, A. Blencowe, M. P. van
publish these results. A. Bansal acknowledges CSIR, New Delhi Koeverden, F. Caruso and G. G. Qiao, ACS Macro Lett.,
for providing the nancial support in terms of research fellow- 2012, 1, 1020–1023.
ship. Raghuvir Singh and G. M. Bahuguna, C. D. Sharma, San- 25 N. V. Alfredo, N. E. Jalapa, S. L. Morales, A. D. Ryabov,
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spectra for FTIR, XRD, TGA, GPC and SEM respectively. 45, 8135–8146.
26 (a) W. Jakubowski and K. Matyjaszewski, Angew. Chem., Int.
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21196 | RSC Adv., 2015, 5, 21189–21196 This journal is © The Royal Society of Chemistry 2015