1.

0 Characterization of TiO2/Graphene Nanocomposites

X-ray powder diffraction (XRD) was a rapid analytical technique widely used for phase
identification of a crystalline material. Other than that, it also provided information on unit cell
dimensions. The prepared TiO2 and TiO2-GO nanocomposites were undergoing X-ray diffraction
and recorded on a Bruker AXS D8 advanced X-ray powder with Cu Kα radiation (l ¼ 1.5418 A).
The obtained XRD patterns were taken to make comparison with JCPDSs (Joint Committee on
Powder Diffraction Standards) cards. The X-ray diffraction patterns of the TiO2-GO
nanocomposites were shown in the Figure 1. There were several peaks identified for TiO2-GO
nanocomposites. All the peaks were assigned to anatase TiO2 (JCPDS no. 04- 016-2837). In the
samples without any contribution of rutile or brookite phase, anatase phase was mainly detected.
In order to calculate the crystallise sizes of the samples, the Debye Scherrer equation was used.
The average crystallise size for the samples was calculated and found to be 11nm. This represents
that the anchoring of GO with TiO2 NPs had only little influence on the crystallise size of phase
structure of TiO2 NPs. (Yadav & Kim, 2016)

Figure 1: XRD patterns of graphene oxide-TiO2 nanocomposites (Yadav & Kim, 2016)

In order to calculate the surface area of the nanocomposites, the Autosorb-1 Quantachrome
Instruments analyzer and the Brunauer-Emmett-Teller (BET) method were used. BET was
commonly used to explain the physical adsorption of gas molecules on a solid surface and it was
a vital analysis technique to determine the surface area of a material. The nitrogen, N2 adsorption-
desorption isotherm was recorded at 77K. The specific surface area of graphene, ozonated
graphene, bare TiO2 and TiO2-OGN-8% were determined by the BET method and tabulated in
Table 1. From Table 1, it clearly indicated that the ozonation leads to a decrease of approximately
82% in the surface area of graphene. Nevertheless, due to the surface area of ozonated graphene
was 3 times larger than TiO2, the addition of 8% wt OGn to TiO2 will eventually produce a
nanocomposite which was 26% higher in surface area. This was consistent with the amount of
OGn added. Increasing in surface area was relatively important key to improve the adsorption
capacity of the nanocomposite. (Suave, Amorim, & Moreira, 2017)

Table 1: Texture characterization of materials. (Suave, Amorim, & Moreira, 2017)

The photoluminescence(PL) emission spectra was used to study the characteristics of

charge carrier trapping, migration, transfer as well as separation and to show the effect of
photogenerated electron and holes in semiconductor during recombination of electrons. The
Hitachi F-4200 fluoresce spectrophotometer was used to record the PL spectra of the samples at
room temperature. The results of PL spectra of pure TiO2 and a representative graphene oxide-
TiO2 nanocomposite, GOT-0.25 showed in the Figure 2 below. The first PL peak existed at around
390nm was due to the band gap of recombination of TiO2 whereas the second PL peak existed at
around 460nm was due to migration of electrons from conduction band to valence band of TiO2.
The results also showed that the presence of graphene oxide(GO) will lower the PL intensity of
the TiO2-GO nanocomposites. The lower PL intensity of the TiO2-GO nanocomposites indicated
that they had a relative low recombination rate of photogenerated electrons and holes under UV
irradiation and abled to prevent direct recombination of photogenerated electron and holes which
electrons moved from valence band to graphene oxide but not moved back to conduction band.
(Yadav & Kim, 2016)
 Figure 2: PL spectra of pure TiO2 and a representative graphene oxide-TiO2 nanocomposite,
GOT-0.25. (Yadav & Kim, 2016)

Thermo gravimetric analysis was used to determine the thermal stability graphene oxide
(GO), graphene, TiO2 and G-TiO2 nanocomposite as well as the effect of TiO2 on graphene sheets.
The TG-DTA (SII-TG/DTA A6300) analysis was carried out to determine the thermal properties
of GO, graphene, TiO2 and G-TiO2. The weight loss in case of pure TiO2 nanoparticle and graphene
oxide were divided into two stages and observed in the Figure 3 below. At below 100℃, the first
stage of weight loss had been observed due to removal of physically absorbed water molecules
whereas the second stage of weight loss had been observed above 200℃ due to decomposition of
graphene oxides. The TGA curve also showed that the total weight loss of G-TiO2 nanocomposite
was only 20% which lesser compare with pure TiO2 and GO which had 35% and 65% respectively.
Hence, the decomposition of graphene oxide to graphene in nanocomposite will lead to improve
the thermal stability of G-TiO2 nanocomposites. (Shanmugam, Alsalme, Alghamdi & Jayavel,
2016)
 Figure 3: Thermo gravimetric curves of graphene oxide(GO), graphene(G), G-TiO2
nanocomposites and pure TiO2. (Shanmugam, Alsalme, Alghamdi & Jayavel, 2016)

The morphology and particles size were characterized by Transmission Electron

Microscope(TEM) and High Resolution Transmission Electron Microscope(HR-TEM). TEM and
HR-TEM were used to observe the crystal structure and graphite layer arrangement by transmitting
electrons through the sample. HR-TEM allowed high-magnification studies of nanomaterials and
its high resolution made it perfect for imaging materials on the atomic scale. Graphene-TiO2
nanocomposites were analyzed with Transmission Electron Microscope(TEM) (Technai F20 G2,
FET) and High Resolution Transmission Electron Microscope(HR-TEM). The figures below
showed the images of TEM analysis of anatase TiO2 nanoparticles and graphene oxide -TiO2
composite material. It exhibited a non-spherical morphology while the average diameter of TiO2
nanoparticles were within 10-15nm. There were no large aggregates and the graphene oxide sheets
were easily observed along with the TiO2 nanoparticles in Figure 4(b). The TiO2 nanoparticles
were well dispersed on the sheets and showed good adherence. (Yadav& Kim,2016)
 .

Figure 4: TEM analysis of (a) anatase TiO2 nanoparticles and (b) graphene oxide -TiO2
composite material. (Yadav & Kim, 2016)

The figures below showed the HR-TEM images of folded and transparent 2D graphene–TiO2
nanocomposites and the higher magnification images respectively. At higher magnification, the
graphene could be observed in layered structure and the TiO2 nanoparticles were marked with red
circle in Figure 5(b). Besides, the crystalline nature of TiO2 nanoparticles and the amorphous
nature of graphene were shown in the Figure 5(b). (Shanmugam, Alsalme, Alghamdi & Jayavel,
2016)

Figure 5: (a) HR-TEM images of G-TiO2 nanocomposites and (b) High magnification of HR-
TEM images. (Shanmugam, Alsalme, Alghamdi & Jayavel, 2016)
 The crystalline nature of the TiO2 nanoparticles was observed by lattice fringes with clear
spacing which shown in the figure below. Figure 6 showed the lattice fringe pattern of TiO2
nanoparticles and its calculated width is 0.35nm for (101) plane. (Shanmugam, Alsalme, Alghamdi
& Jayavel, 2016)

Figure 6: Lattice fringe pattern of TiO2 nanoparticles. (Shanmugam, Alsalme, Alghamdi &
Jayavel, 2016)

Reduced graphene oxide-TiO2 nanocomposites could be prepared in different methods which

were direct sol-gel method and hydrothermal method. Figure 7 and Figure 8 showed the TEM
images of Graphene-TiO2 nanocomposites prepared by direct sol-gel method and hydrothermal
method respectively. The sample prepared by direct sol-gel method gave well dispersed TiO2
nanoparticles on the RGO surface while the sample prepared by hydrothermal method presented
a more heterogeneous structure with larger and agglomerated TiO2 particles. (Atout, Alvarez,
Chebli, Bouguettoucha, Tichit, Llorca & Medina, 2017)
 Figure 7: (a)&(b) TEM images of Graphene-TiO2 nanocomposites prepared by direct sol-gel
method. (Atout, Alvarez, Chebli, Bouguettoucha, Tichit, Llorca & Medina, 2017)

Figure 8: (a)&(b) TEM images of Graphene-TiO2 nanocomposites prepared by hydrothermal

method. (Yang, Sun, Li, Wang & Song, 2016)

On the other hand, Graphene-TiO2 nanocomposites were also analysed with Scanning Electron
Microscope(SEM). SEM was used to examine the length, diameter and morphology of the sample
by scanning it with a focused beam of electrons. Figure 9 showed the SEM images of G–TiO2
nanocomposite. From the SEM images, TiO2 nanoparticles dispersed on at the edge and interlayer
of the wrinkles and folded like structure of graphene sheets. In figure 9(b) which was the high
magnification of SEM images, no agglomeration of TiO2 nanoparticles was observed in the G–
TiO2 nanocomposites. Besides, the SEM images of nanocomposites revealed the non-spherical
morphology of TiO2 nanoparticles existed on graphene sheet. (Shanmugam, Alsalme, Alghamdi
& Jayavel, 2016)

Figure 9: SEM images of graphene–TiO2 nanocomposites. (Shanmugam, Alsalme, Alghamdi

& Jayavel, 2016)

With modification of reduced graphene oxide, TiO2 nanocomposites will show different
morphology. Figure 10 below showed the SEM images of TiO2 and TiO2– RGO nanocomposite.
TiO2 shows ball like structure which consisted of numerous nanoribbons with 600nm in diameter.
In figure 10(b), it was clearly shown that the reduced graphene oxide sheets were wrapped on the
TiO2 ball surface after RGO modification. This modification resulted the rough and non-spherical
surface of the Graphene-TiO2 nanocomposites. (Yang, Sun, Li, Wang & Song, 2016)
 Figure 10: SEM images of (a)TiO2 and (b)TiO2– RGO nanocomposite. (Yang, Sun, Li,
Wang & Song, 2016)

The UV-Vis Diffraction Reflectance Spectroscopy (DRS) was implemented to measured

the optical properties of pure TiO2 (PT) and different weight percentage of graphene oxide (GO)
in composite with TiO2. It was observed all the spectra exhibit the absorption band around 390nm
due to the presence of TiO2. Increasing absorption in visible light region and darkening physical
appearance of samples were in positive relationship with the increasing wt% of GO for 0, 0.25,
0.5, 1.0 and 2.0 wt % as shown in Figure 11 below. (Yadav & Kim, 2016)

Figure 11: UV-Vis DRS spectra of graphene oxide-TiO2 nanocomposites. (Yadav & Kim, 2016)
 The solid state UV-vis absorbance was carried out to observe the alteration of band gap of
pure TiO2 and TiO2 composite with 10 wt% of GO prepared by T/G (sol-gel method) and T/GS
(hydrothermal route). The diffuse reflectance UV-vis spectra (DRS UV-vis) of pressed powder
sample diluted with KBr were recorded on a Shimadzu (UV-3600 spectrophotometer with a
Harrick Praying Mantis accessory) and determined by Kubelka-Munk. From the Figure 12 below,
a clear blueshift and redshift in maximum adsorption edge were observed in the TiO2-GO
composites, which leaded to reduction of band gap from 3.26 eV to 3.1 eV. This due to the
interaction between Ti and C atoms which will reduce the recombination of photo-generated
electron-hole pairs and increased the absorption properties. (Atout, Alvarez, Chebli,
Bouguettoucha, Tichit, Llorca & Medina, 2017)

Figure 12: Diffuse reflectance absorption of TiO2, T/G-10 and T/GS-10. (Atout, Alvarez, Chebli,
Bouguettoucha, Tichit, Llorca & Medina, 2017)
 The Energy-dispersive X-ray spectroscopy (EDX) was used to analyse the chemical
element present in the sample by collecting the photons (X-ray) emitted using X-ray detector.
From the Figure 13 below showed significant peaks of C, O, Pd and Ti only, indicated the
nanocomposite sample had high purity. (Yang, Sun, Li, Wang & Song, 2016)

Figure 13: EDX spectrum of TiO2-RGO-Pd composite. (Yang, Sun, Li, Wang & Song, 2016)

X-ray photoelectron spectroscopy (XPS) was a surface-sensitive quantitative spectroscopic

technique to measure the elemental composition of a material. The binding energy of the material
was analyzed by XPS spectra recorded using ESCA 3400, SHIMADZU. The XPS analysis could
display in convolution and deconvolution type of spectra for study purpose. In convolution
spectrum as shown in the Figure 14(a) below displayed all the element presence in a material. The
C: O: Ti ratio of the composite was 73.02, 22.56 and 4.42% as observed from the convolution
spectrum. Whereas in Figure 14(b), deconvolution XPS spectrum of C1s, three peaks of 285.12eV,
282.27eV and 288.47eV were observed due to the presence of C=C, Ti-C and C=O bonds
respectively. Figure 14(c) showed O1s electron exhibits a peak of 532.15eV binding energy. In
Figure 14(d) spectrum was used to determine the presence of Ti with the binding energy 2p
electrons by comparing the peaks of Ti2p1/2 and Ti2p3/2 exhibiting value of 464.57 and 459.37 eV
binding energy respectively with the pure Ti4+ anatase structure. (Shanmugam, Alsalme, Alghamdi
& Jayavel, 2016)

Figure 14: XPS spectra of G-TiO2 nanocomposite. (Shanmugam, Alsalme, Alghamdi & Jayavel,
2016)

Raman spectroscopy was used to provide molecular fingerprint of materials and was
performed at room temperature using a Raman Microprobe (Renishaw RM1000) with 514 nm
laser light. Raman scattering was used to authorize the reduction of GO due to the sensitive
electronic structure of graphene. From the Figure 15 below showed the three Raman spectra
of GO, TiO2-RGO and TiO2-RGO-Pd nanocomposite and all of them exhibited two main band
at 1600 (G band) and 1350 cm-1 (D band). The intensity ratio of D and G band (ID/ IG) was an
indication of the reduction process. The intensity ratio of TiO2-RGO and TiO2-RGO-Pd
nanocomposite were 1.12 and 1.21 respectively, which was much higher than GO (0.91),
which indicateed the higher effectiveness of reduction of graphene oxide in hydrothermal
 treatment. Furthermore, the two small peaks of A1g and Eg of anatase TiO2 that located at 522
and 639 cm-1 were observed in the spectra of TiO2-RGO and TiO2-RGO-Pd nanocomposite.
(Yang, Sun, Li, Wang & Song, 2016)

Figure 15: Raman spectra of GO, TiO2-RGO and TiO2-RGO-Pd nanocomposite. (Yang,
Sun, Li, Wang & Song, 2016)

Fourier-transform infrared spectroscopy (FT-IR) was used to obtain an infrared spectrum

of absorption and emission of solid, liquid, and gas. The Alpha Bruker FT-IR spectrophotometer
was used to determine the FT-IR spectra. Figure 16 showed the FT-IR spectra of TiO2 nanoparticle
and G-TiO2 nanocomposites. The black line represented spectrum of TiO2 particle while red line
represent spectrum of G-TiO2 nanocomposites. At 3000cm-1 to 3500cm-1, there was a board peak
which was presence of hydroxyl group (O-H group). At 500cm-1 to 1000cm-1, wide absorption and
high intensity peaks were assigned to the vibration of O-Ti-O bond. At 3500 cm-1 spectrums, a
weak intensity broad peak showed the O-H bond of the G-TiO2 nanocomposites. At peak of
1606cm-1, the spectrum was corresponding to Carbon= carbon double bond (C=C bond) while O-
Ti-O bond and vibration of TiO2 was showed at the peak below 1000cm-1. Therefore, FT-IR
spectra could confirm the formation of G-TiO2 nanocomposites. (Shanmugam, Alsalme, Alghamdi
& Jayavel, 2016)

Figure 16: FT-IR spectra of TiO2 nanoparticle and G-TiO2 nanocomposites.

(Shanmugam, Alsalme, Alghamdi & Jayavel, 2016)

2.0 Mechanism of photodegradation

The photocatalytic activity of the synthesized G-TiO2 nanocomposites was analysed using
methylene blue (MB) dye under UV and visible light irradiation. During the light irradiation,
photo-induced electrons and holes were excited on the conduction band and valence band of TiO2
respectively. The electron was then transferred to the surface of TiO2 and reacted with the
functional group of reduced graphene to produce oxide radical (O2∙) by reduction reaction of
conduction band, while the hole reacted with hydroxyl to produce hydroxyl radical (OH∙) by
oxidation process of valence band. The resulting O2∙ and OH∙ radicals played most important factor
to determine the performance of MB dye degradation. (Shanmugam, Alsalme, Alghamdi &
Jayavel, 2016)
 With the addition of graphene will increase the performance of photodegradation process.
Graphene in the composite was acting like an electron tank, to store the photo-induced electrons
transported from TiO2 due to its highest electron mobility theory. During the photodegradation
process, the graphene was acted like a medium to reduce the recombination of the photo-generated
electron-hole pair by forcing and redirecting the photo-induced electrons to move through
graphene sheets to prolong the recombination time, which leaded to an improved photo-conversion
efficiency. (Shanmugam, Alsalme, Alghamdi & Jayavel, 2016)

Figure 17: Mechanism of photodegradation of MB dye molecule due to the G-TiO2

nanocomposite. (Shanmugam, Alsalme, Alghamdi & Jayavel, 2016)
REFERENCES:
Yadav, H. M., & Kim, J. S., 2016. Solvothermal synthesis of anatase TiO2-graphene oxide
nanocomposites and their photocatalytic performance. Journal of Alloys and Compounds, pp.123-
129.

Shanmugam, M., Alsalme, A., Alghamdi, A., & Jayavel, R., 2016. In-situ microwave synthesis of
graphene–TiO2 nanocomposites with enhanced photocatalytic properties for the degradation of
organic pollutants. Journal of Photochemistry & Photobiology, B: Biology, pp. 216-223.

Suave, J., Amorim, S. M., & Moreira, R. F. P. M., 2017. TiO2-graphene nanocomposite supported
on floating autoclaved cellular concrete for photocatalytic removal of organic compounds. Journal
of Environmental Chemical Engineering, pp. 3215-3223.

Atout, H., Alvarez, M. G., Chebli, D., Bouguettoucha, A., Tichit, D., Llorca, J., & Medina, F.,
2017. Enhanced photocatalytic degradation of methylene blue: Preparation of TiO2/reduced
graphene oxide nanocomposites by direct sol-gel and hydrothermal methods. Materials Research
Bulletin, pp. 578-587.

Yang, R., Sun, C. G., Li, K. X., Wang, L. T., Song, M. J., 2016. Preparation of TiO2-reduced
graphene oxide-Pd nanocomposites for phenol photocatalytic degradation. Ceramics International,
pp. 1339-1344.