Part 1: Optical properties of TiO2/graphene nanocomposites by difference analysis

1. Crystalline properties

XRD analysis

X-ray powder diffraction (XRD) is a rapid analytical technique widely used for phase
identification of a crystalline material. Other than that, it also can provide 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 are shown in the Figure 1. There are several peaks identified for TiO2-GO
nanocomposites. All the peaks were assigned to anatase TiO2 2 (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 has 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)
 2. Surface area properties

BET

In order to calculate the surface area of the nanocomposites, the Autosorb-1

Quantachrome Instruments analyzer and the Brunauer-Emmett-Teller (BET) method is used.
BET is commonly used to explain the physical adsorption of gas molecules on a solid surface
and it is 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 indicates 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 is 3 times larger than TiO2, the addition of 8% wt OGn to TiO2 will
eventually produces a nanocomposite which is 26% higher in surface area. This is consistent
with the amount of OGn added. Increasing in surface area is 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)

3. Electronic properties

Photoluminescence measurement

The photoluminescence(PL) emission spectra is 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 can be implemented 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 show in the Figure 2 below. The first PL peak
exists at around 390nm is due to the band gap of recombination of TiO2 whereas the second PL
peak exists at around 460nm is due to migration of electrons from conduction band to valence
band of TiO2. The results also show 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 indicate that they have a relative low recombination rate of photogenerated
electrons and holes under UV irradiation and able to prevent direct recombination of
photogenerated electron and holes which electrons move from valence band to graphene oxide
but not move 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)

4. Thermal properties

TGA analysis

Thermo gravimetric analysis is used to determine the thermal stability graphene oxide
(GO), graphene, TiO2 and G-TiO2 nanocomposite as well as the influence of TiO2 on graphene
sheets. The TG-DTA (SII-TG/DTA A6300) analysis is 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 are divided into two stages and observed in the Figure 3 below.
At below 100℃, the first stage of weight loss has been observed due to removal of physically
absorbed water molecules whereas the second stage of weight loss has been observed above
200℃ due to decomposition of graphene oxides. The TGA curve also shows that the total weight
loss of G-TiO2 nanocomposite is only 20% which lesser compare with pure TiO2 and GO which
has 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)

5. Morphology and particle size properties

TEM & SEM analysis

Graphene-TiO2 nanocomposites are analyzed with Transmission Electron Microscope(TEM)

(Technai F20 G2, FET) and High Resolution Transmission Electron Microscope(HR-TEM). The
figures below show the images of TEM analysis of anatase TiO2 nanoparticles and graphene
oxide -TiO2 composite material. It exhibits a non-spherical morphology while the average
diameter of TiO2 nanoparticles are within 10-15nm. There are no large aggregates and the
graphene oxide sheets are easily observed along with the TiO2 nanoparticles in Figure 4(b). The
TiO2 nanoparticles are well dispersed on the sheets and shows 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 show the HR-TEM images of folded and transparent 2D graphene–TiO2
nanocomposites and the higher magnification images respectively. At higher magnification, the
graphene can be observed in layered structure and the TiO2 nanoparticles are marked with red
circle in Figure 5(b). Besides, the crystalline nature of TiO2 nanoparticles and the amorphous
nature of graphene are also 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 is observed by lattice fringes with clear
spacing which shown in the figure below. Figure 6 shows 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 can be prepared in different methods which

are direct sol-gel method and hydrothermal method. Figure 7 and Figure 8 shows 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 gives well dispersed TiO2
nanoparticles on the RGO surface while the sample prepared by hydrothermal method presents 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 are also analysed with Scanning Electron
Microscope(SEM). Figure 9 shows the SEM images of G–TiO2 nanocomposite. From the SEM
images, TiO2 nanoparticles disperse on at the edge and interlayer of the wrinkles and folded like
structure of graphene sheets. In figure 9(b) which is the high magnification of SEM images, no
agglomeration of TiO2 nanoparticles is observed in the G–TiO2 nanocomposites. Besides, the
SEM images of nanocomposites reveals the non-spherical morphology of TiO2 nanoparticles
existing 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 show the SEM images of TiO2 and TiO2– RGO nanocomposite.
TiO2 shows ball like structure which consists of numerous nanoribbons with 600nm in diameter.
In figure 10(b), it is clearly shown that the reduced graphene oxide sheets are wrapped on the
TiO2 ball surface after RGO modification. This modification results 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)
 6. Optical properties:
i. UV-vis diffuse reflectance spectroscopy test

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

optical properties of pure TiO2 (PT) and different weight percentage of graphene oxide (GO) in
composite with TiO2. It is 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 are in positive relationship with the increment of wt% of GO as shown in
Figure 11 below. (Yadav & Kim, 2016)

Figure 11: UV-Vis DRS spectra of graphene oxide-TiO2 nanocomposites. (Yadav & Kim, 2016)

ii. Solid state UV-vis absorbance test

The solid state UV-vis absorbance is 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 determine by Kubelka-Munk. From the Figure 12 below,
a clear blueshift and redshift in maximum adsorption edge are observed in the TiO2-GO
composites, which leads 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 increase 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)

7. Chemical Element Properties

1. EDX

The Energy-dispersive X-ray spectroscopy (EDX) is used to analyze the chemical element
present in the sample by collecting the photons (X-ray) emitted using X-ray detector. From the
Figure 13 below shows significant peaks of C, O, Pd and Ti only, indicating the nanocomposite
sample has high purity. (Yang, Sun, Li, Wang & Song, 2016)
 Figure 13: EDX spectrum of TiO2-RGO-Pd composite. (Yang, Sun, Li, Wang & Song, 2016)

2. XPS

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

technique to measure the elemental composition of a material. The binding energy of the material
is analyzed by XPS spectra recorded using ESCA 3400, SHIMADZU. The XPS analysis can
display in convolution and deconvolution type of spectra for study purpose. In convolution
spectrum as shown in the Figure 14(a) below display all the element presence in a material. The
C: O: Ti ratio of the composite is 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 are observed due to the presence of C=C, Ti-C and C=O bonds
respectively. Figure 14(c) shows O1s electron exhibits a peak of 532.15eV binding energy. In
Figure 14(d) spectrum is 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)

8. Chemical bonding properties

I. XPS analysis

X-ray photoelectron spectroscopy (XPS) is also known as electron spectroscopy for

chemical analysis (ESCA). In this XPS analysis, XPS is used to show the XPS spectra of G-TiO2
nanocomposite as in diagram 1.0. The survey spectrum in diagram 1(a) showed all elements of
composites. In this XPS analysis, the ratio of C: O: Ti composite percentage was 73.02, 22.56
and 4.42. In figure 1(b), the analysis shows the deconvolution XPS spectrum of C1s. The
prominent peak with value of 285.12eV showed the graphetic carbon-carbon double bond (C=C).
At peak of value 282.37eV, showed the binding of Titanium-carbon bond (Ti-C). At peak of
value of 288.47eV, showed the binding state of carbon-oxygen bond (C=O). Next, in
diagram1(c) showed the O1s electron spectrum with binding energy of 532.15eV. In diagram
1(d), XPS spectrum used to confirm the presence of Ti. The peak with binding energy of
464.57eV showed the Ti 2p1/2, while the peak with binding energy of 459.37eV showed the Ti
2p3/2. These two peaks are in good arrangement with the binding energy value of Ti4+ of pure
anatase structure. (Shanmugam, Alsalme, Alghamdi & Jayavel, 2016)

Diagram1.0: XPS spectra of G-TiO2 nanocomposites. (Shanmugam, Alsalme, Alghamdi

& Jayavel, 2016)

II. FT-IR analysis

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

absorption and emission of solid, liquid, and gas. The Alpha Bruker FT-IR spectrophotometer is
used to determine the FT-IR spectra. Figure 16 showed the FT-IR spectra of TiO2 nanoparticle
and G-TiO2 nanocomposites. The black line represent spectrum of TiO2 particle while red line
represent spectrum of G-TiO2 nanocomposites. At 3000cm-1 to 3500cm-1, there is a board peak
which is presence of hydroxyl group (O-H group). At 500cm-1 to 1000cm-1, wide absorption and
high intensity peaks are assigned to the vibration of O-Ti-O bond. At 3500 cm-1 spectrums, a
weak intensity broad peak shows the O-H bond of the G-TiO2 nanocomposites. At peak of
1606cm-1, the spectrum is corresponding to Carbon= carbon double bond (C=C bond) while O-
Ti-O bond and vibration of TiO2 is showed at the peak below 1000cm-1. Therefore, FT-IR
spectra can 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)
Part 2: Mechanism of photodegradation

The photocatalytic activity of the synthesized G-TiO2 nanocomposites is analysed using

methylene blue (MB) dye under UV and visible light irradiation. During the light irradiation,
photo-induced electrons and holes are excited on the conduction band and valence band of TiO2
respectively. The electron is then transferred to the surface of TiO2 and react with the functional
group of reduced graphene to produce oxide radical (O2∙) by reduction reaction of conduction band,
while the hole reacts with hydroxyl to produce hydroxyl radical (OH∙) by oxidation process of
valence band. The resulting O2∙ and OH∙ radicals play 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 is 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 is acting 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 leads 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.