CORRECTION TABLE ACCORDING TO REVIEWERS COMMENTS

REVIEWER COMMENTS CORRECTION

Reviewer 1 1. Language.  The English of the manuscript was revised and checked.
The language is a bit weak. You need to get
the manuscript checked from an English
speaking native or get help from services.
2. Section Abstract (Line 2) Section Abstract (Line 2)
Language error.  The sentence was changed to:
Amongst these polymorphs, “brookite films “Amongst these polymorphs, brookite are less reported and
often” less reported and mostly produced as mostly produced as a by-product.”
a by-product.
3. Section Abstract (Line 3) Section Abstract (Line 3)
Language error.  The sentence was changed to:
In this work, two deposition methods which “In this work, two deposition methods which are dip and spin
are dip and spin coating are selected “to coating are selected to compare the effect of deposition
compare on the effect” of deposition methods on TiO2 crystalline phase formation, particularly on
methods towards phase formation. identifying the brookite presence.”
4. Section Introduction (Paragraph 3, Line 7) Section Introduction (Paragraph 3, Line 7)
Check language.  The sentence was changed to:
For instance, during a dip coating, the glass “For instance, during a dip coating, the glass substrate is
substrate is normally withdrawn vertically normally withdrawn vertically from the sol at a constant
from the sol at a “continues” speed. speed.”
5. Section Introduction (Paragraph 4, Line Section Introduction (Paragraph 4, Line 19)
19)  This statement is to highlight an argument that a single
“In another method, Mothi et al. managed to phase brookite film is able to be produced via spin coating
synthesize brookite particle with crystallite method as reported by Arier and Tepehan [22].
size of 11 nm via spin coating using TTIP as  This is because in Arier and Tepehan work, brookite is
a precursor and ethylene glycol as a produced as single phase. In contrast, Mothi et al. produced
complexing agent [22].” brookite in a mixture phase.
 The argument was revised to:
“For instance, Arier and Tepehan managed to synthesize
 brookite thin film (with crystallite size of ~12 nm) on Corning
2947 glass substrate using titanium butoxide as a precursor
and ethanol as a solvent [37].”
6. Section Introduction (Paragraph 4) Section Introduction (Paragraph 4)
The question is that why in this work brookite  The paragraph 4 was revised in order to highlight the
is not formed via sol-gel. Please discuss this brookite formed via sol-gel dip and spin coating.
in the results and discussion section.  The paragraph was revised as follow:
“In reviewing related works on TiO2 deposition, few reported
work are discussing on the effect of deposition method on
the produced TiO2 phases. Many works are just simply
mentioning the deposition method and phases produced
without focusing on explaining the effect of the deposition
method on the results obtained. In focus to brookite
formation, several deposition methods such as dip coating
and spin coating had produce this crystalline phase as a
minor product or mixture phases. For example, using the dip
coating method, the produced TiO2 film deposited on the
glass substrate contained brookite as a by-product to
anatase [33]. While, TiO2 films with the 70% weight fraction
of brookite with the remaining fractions were anatase and
amorphous TiO2 produce by Djoued et. al. [34]. Djoued et al.
claimed that the amount of polyethylene glycol (PEG) in the
sol formulation influenced the nucleation of the brookite and
anatase phases. In addition, Ohara and his co-workers
observed an overlapping of crystalline peaks of brookite
(120) and anatase (101) in TiO 2 film deposited on soda lime
glass [35]. He suggests that the Na ion from the substrate
diffused to the film surface and promotes the brookite phase.
Despite less report on a single brookite formation, Novotna
et al. had observed formation of single brookite film on soda
lime glass substrate with crystallite size of 50 ± 10 nm [36].
He claimed that the diffusion Na+ lead to the formation of
 brookite. While, using the spin coating method, more work
had been able to synthesize single brookite film. For
instance, Arier and Tepehan managed to synthesize
brookite thin film (with crystallite size of ~12 nm) on Corning
2947 glass substrate using titanium butoxide as a precursor
and ethanol as a solvent [37]. Besides, Komaraiah et al. had
reported producing brookite film on glass substrate with
crystallite sizes of 54 - 67 nm [16]. Singh et al. had also
produced brookite film with crystallite size of 28 – 48 nm via
spin coating using ethyl alcohol as a solvent [38]. While,
Katsumata et al. reported brookite formation in film
deposited on polyimide substrate. Here, the brookite
formation is due to the concentration of Na ion from sodium
oleate during hydrothermal treatment [39].”
7. Section Introduction (Paragraph 5, Line 7) Section Introduction (Paragraph 5, Line 7)
“A more systematic study on the deposition  The reference number was added.
method was made by Wang et al. to “Besides, Wang et al. had carried out study on different
understand the effect of deposition method deposition method to understand its effect on the TiO 2 thin
on the TiO2 thin film phase formation, grain film phase formation, grain size, morphology and thickness
size, morphology and thickness towards towards greater photocatalytic performance [29].”
greater photocatalytic performance”. Put
reference in this sentence too.
8. Section Introduction (Paragraph 2, Line Section Introduction (Paragraph 2, Line 28)
28)  The sentences was added and revised in order to highlight
Does green sol-gel route produces brookite? the green sol-gel route (without the use of any solvent).
If yes, mention the reference.  The senteces was revised as follow:
“Yet, there are no published report on the brookite formation
without the use of solvent. Therefore, this work is
pioneering an effort on TiO2 deposition for brookite
formation via a green sol-gel route.”
9. Section Introduction (Paragraph 1, Line 6) Section Introduction (Paragraph 1, Line 6)
Add more information on the applications of  More information on the photocatalytic activity of brookite
 brookite phase. has been added as follow:
“Nevertheless, studies have also shown that brookite phase
has notably better in photocatalytic performance as
compared to those of rutile and anatase [6-14]. For example,
Mukarami et al. shows that the brookite powder produced
1100 ppm in 500 min for photocatalytic decomposition of
acetaldehyde and exhibit higher photocatalytic activity
compared to the other TiO2 powders [9]. In addition, Kandiel
et al. had reported that the brookite nanoparticles produced
~17% photonic efficiency which is higher than anatase in
methanol photooxidation reaction [7]. Tran et al. had also
compared the photocatalytic activity of brookite, anatase and
rutile in the pharmaceutical ibuprofen (IBP), the recalcitrant
phenol (Ph), and the more reactive cinnamic acid (CA) [6].
The results show that the mineralization shows of brookite
(51%) > anatase (50%) > rutile (7%) for photocatalytic
degradation in IBP, brookite (15%) > anatase (13%) > rutile
(3%) for photocatalytic degradation in Ph and brookite (52%)
> anatase (36%) > rutile (38%) for photocatalytic
degradation in CA, respectively [6]. Meanwhile, for the
brookite film, Alotaibi et al. shows that the brookite film has
four times (1.17 x 10-4 molecules per incident photon)
superior photocatalytic activity in the destruction of stearic
acid compared to an anatase film [15]. Komariah et al. also
reported that the brookite film shows 92% photocatalytic
degradation of methylene blue after 240 min under visible
light irradiation [16].”
10. Section Results and discussion Section Results and discussion (Paragraph 2, Line 12)
(Paragraph 2, Line 10)  The match JCPDS no. has beed included in the Table 2.
Match your JCPDS no with those given in
other papers mentioned in Introduction (give
references) for spin and sol-gel. Mention the
 differences in your results as to the phases
formed, angle and orientation.
11. Section Results and discussion Section Results and discussion (Paragraph 2, Line 12)
(Paragraph 2, Line 12)  Table 2 has been added as suggested.
Show from previous references, that a single
phase brookite is formed via either spin or
other coating techniques. Which authors
have been successful in doing so and what
were their results. You may make a table to
show comparison of your work with theirs.
12. Section Results and discussion Section Introduction (Paragraph 2)
You need to prove that how your green sol  The novelty of green sol-gel route is highlight in Introduction
gel route work is novel and different from section, Paragraph 2.
others  The paragraph 2 was revised as follow:
“Many techniques available to deposit the TiO 2 thin films
which are hydrothermal treatment, pulsed laser deposition
[17], chemical vapour deposition [15], vapor phase [18],
spray pyrolysis [19] and sol-gel process [16]. In sol-gel
process, the precursor, solvent, catalyst and water plays a
remarkable role in the synthesis of TiO2 thin film [20].
Hafizah et al. stated that the precursor such as titanium (IV)
isopropoxide (TTIP), titanium tetrachloride (TiCl 4), titanium
tetrabutoxide (TBT) and titanium alkoxides serves to
develop the TiO2 polymorphs and its crystallinity [21]. Based
on different precursors, TTIP is widely used in sol-gel
process due to generating stable solution at low hydrolysis
ratio [20]. In another hand, catalyst serves to growth and
influence the type of phase’s formation as well as its
crystallite size. Meanwhile, solvent attends to slow the rate
of the hydrolysis and condensation in the sol-gel process
that consequently influence the films crystallization, films
microstructures, crystallite sizes as well as their photo
 electrochemical properties [22]. For example, Mahyar and
Amani-Ghadim reported that ethanol favourable to
produced mixture of anatase and rutile with crystallite size
of 14.5 nm and lowest specific surface area, 9.07 m 2g-1 [23].
Thus in common, solvent is widely used for almost all sol
formulation during TiO2 thin film deposition. However, it
should be highlighted that the long term exposure to
solvents can be toxic and harmful to the environmental and
human body. This is because, solvents consist of different
chemical groups which lead to difference properties
especially in the physiological and toxicological aspects
[24]. For instance, used of benzene can caused cancer in
humans [25]. Moreover, Uzma et al. [26] and Rama et al.
[27] also stated that the solvents exposure lead to damage
on respiratory, haematological and thyroid functioning. For
this reason, researchers had started to initiate work on a
green chemistry approach for TiO2 synthesis. Recently, a
systematically work carried out as an attempt to produce
sol-gel TiO2 thin films with the desired grain size and
preferable phases without the use of solvent had been
reported by Yazid et al. [20]. Also, Spada et al. had
managed to produce anatase and rutile TiO2 nanoparticles
without the use of any solvents [28]. Yet, there are no
published report on the brookite formation without the use
of solvent. Therefore, this work is pioneering an effort on
TiO2 deposition for brookite formation via a green sol-gel
route.”
13. Section Results and discussion Section Results and discussion
There are no references in your results  Reviews on related work on brookite formation is summarize
supporting the phase from with respect to in Table 1 and Table 2.
the type of coating and the reasons for such  Section Results and discussion was revised.
behavior in the discussion section. This
 infers that there is no discussion and the
peers in your field are not acknowledged.
Which is why the manuscript length and
especially the results section is too weak and
or less content. It is mere of observation
only.
14. Section Results and discussion Section Results and discussion (Paragraph 5)
(Paragraph 5)  The paragraph 5 is discussing on the effect of deposition
Give reasons or possible inference for these method of dip and spin coating.
results “Thus, it can be confirmed that  The effect of temperature is to be discussed according to
anatase and rutile are presence in the TiO2 each deposition method, respectively.
thin film produced via dip coating at 300°C “Fig. 4 displays the TEM microstructures of the TiO 2 thin
and only brookite is presence in the TiO2 thin films deposited via dip coating. It is obvious that the
films produced via spin coating at both deposited TiO2 thin film had a spherical shape with a lattice
temperature of 200°C and 300°C.” fringes of 0.35 nm and 0.33 nm which can be assigned to
the d-spacing of the of anatase (101) and rutile (110),
respectively [51-52]. Meanwhile, Fig. 5 shows the TEM
microstructures of the TiO2 thin films deposited via spin
coating. As shown in the figures, the microstructures had a
spherical shape with lattice fringes of 0.28 nm which belong
to the (111) plane of brookite [51-52]. Thus, it can be
confirmed that anatase and rutile are presence in the TiO2
thin film produced via dip coating and only brookite is
presence in the TiO2 thin films produced via spin coating.”
Reviewer 2 1. Section Results and discussion Section Results and discussion (Paragraph 1, Line 17)
(Paragraph 1, Line 17)  The discussion on the absence/not observed crystalline
For spin coating, why increase the phase at 400°C and 500°C was carried out in paragraph 1
temperature to 400°C and 500°C, the (line 17).
crystallite presence is vanished?  The discussion as follow:
“The absence of brookite phase formation at high
temperature (400°C and 500°C) could be due to its
thermodynamically metastable character where it is
 preferably existing at low temperature [45]. This is also
aligned with the finding reported by Allen et al. where in their
work, 39.7% brookite crystalline phase at 110°C had
reduced to 15.1% when the temperature is increased at
600°C [46]. In addition, brookite is not identified at
temperature 700°C and above [46]. The similar observation
is also obtained by Li et al. where the amount of brookite
decreased when the temperature was increased from 200°C
to 400°C with the crystallite size < 10 nm and until it did not
identify above 400°C [47]. The absence of the TiO 2
crystalline phase could be due to the no solvent use in the
sol formulation. Solvent serves to slow the rate of the
hydrolysis and condensation in the sol-gel process. Herman
et al. reported that the desorption temperature for water is
lower (~250 K) compared to methanol (610 K) [48]. Thus, in
this work where no solvent is used, it is expected the higher
rate of hydration is observed particularly at high temperature
thus crystallization is hindered.”
2. Section Results and discussion Section Results and discussion (Paragraph 1, Line 18)
(Paragraph 1, Line 18)  The discussion on the amorphous material was revised.
Why is an amorphous material presence?  The discussion as follow:
“The absence of brookite phase formation at high
temperature (400°C and 500°C) could be due to its
thermodynamically metastable character where it is
preferably existing at low temperature [45]. This is also
aligned with the finding reported by Allen et al. where in their
work, 39.7% brookite crystalline phase at 110°C had
reduced to 15.1% when the temperature is increased at
600°C [46]. In addition, brookite is not identified at
temperature 700°C and above [46]. The similar observation
is also obtained by Li et al. where the amount of brookite
decreased when the temperature was increased from 200°C
to 400°C with the crystallite size < 10 nm and until it did not
identify above 400°C [47]. The absence of the TiO 2
crystalline phase could be due to the no solvent use in the
sol formulation. Solvent serves to slow the rate of the
hydrolysis and condensation in the sol-gel process. Herman
et al. reported that the desorption temperature for water is
lower (~250 K) compared to methanol (610 K) [48]. Thus, in
this work where no solvent is used, it is expected the higher
rate of hydration is observed particularly at high temperature
thus crystallization is hindered.”