Surfaces and Interfaces 25 (2021) 101227

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Surfaces and Interfaces

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Platinum-alumina modified SO2− 4 -ZrO2/Al2O3 based bifunctional catalyst

for significantly improved n-butane isomerization performance
Ikram Ullah b, T.A. Taha c, d, Asma M. Alenad e, Ikram Uddin f, Asif Hayat a, *, Ashiq Hayat g,
Muhammad Sohail h, *, Ahmad Irfan i, Javid Khan j, Arkom Palamanit k
a
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116, PR China
b
Division of Nanomaterials and Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei
230026, PR China
c
Physics Department, College of Science and Arts, Jouf University, P.O. Box 756, Al-Gurayyat, Saudi Arabia
d
Physics and Engineering Mathematics Department, Faculty of Electronic Engineering, Menoufia University, Menouf 32952, Egypt
e
Chemistry Department, College of Science, Jouf University, P.O. Box: 2014, Sakaka, Saudi Arabia
f
CAS Key Laboratory of Science and Technology on Applied catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, PR China
g
Department of Physics, Quaid-e-Azam University, Islamabad, Pakistan
h
Institute for advanced study, Shenzhen University, Shenzhen 518060, PR China
i
Department of Chemistry, College of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia
j
School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, PR China
k
Energy Technology Program, Department of Specialized Engineering, Faculty of Engineering, Prince of Songkla University, 15 Karnjanavanich Rd., Hat Yai, Songkhla
90110, Thailand

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, sulfated zirconia with loading of platinum (Pt) and platinum alumina (PA-Al2O3) promoted sulfated
n-butane isomerization zirconia (SZ) catalysts were synthesized by hydro-thermal route. The samples were characterized by XRD, BET,
Pt-modified sulfated zirconia FT-IR, NH3-TPD, and TGA. The catalytic efficiency of all the synthesized catalysts was tested on the isomerization
Hydro-thermal synthesis
of n-butane. The results indicated that the conversion of n-butane (71.04%), selectivity to i-butane (98.96%), and
Catalytic performance
Stability
yield of i-butane (70.30%) is significantly high for PA/SZ sample than that of Pt modified SZ and bare SZ. The
results of this study suggest that the SZ modified by Pt/Al2O3 (PA) provided better catalytic performance and
higher stability (within 25 h of TOS), when compared with SZ, and Pt-modified SZ.

1. Introduction
In Petroleum processing, the catalytic transformation of organic
compounds by isomerization route has gained much importance over
the recent years [1]. Although, the isomerization reactions in the pres­
ence of strong solid acidic catalysts were studied [2–4], however, the
problems associated in the presence of acidic liquid complex is still
considered a major challenge limiting catalyst performance [5]. Sulfated
positions, and poor reaction configuration [13]. Previously, Fe, and Mn
were loaded over SZ, which resulted in catalytic complexes with higher
isomerization performance [14]. Ni and La were tested into SZ to
improve the catalytic performance in the isomerization of n-pentane
[15] and n-hexane [16]. Jatia et al. [17] and Adeeva et al. [18] observed
significant and fast deactivation, when SZ promoted with Mg and Fe
were studied. In addition, the clear and remarkable influence wiped out
once the reaction was performed at a temperature greater than 240 C
◦

zirconia (SZ) is used as a support medium and is considered one of the
most favorable metallic oxide, due to its higher catalytic activity in an
acidic environment [6]. SZ has been tested in several reactions; isom­
erization of n-butane [7], pentane [8], n-hexane [9], alkylation [10],
fisher tropsch synthesis [11], and transformation of methanol to organic
compounds [12]. Among several benefits, the use of SZ alone provided
some serious drawbacks, such as fast deactivation, lacking acidic
[19]. Some research groups used Ni loaded SZ for the isomerization
reaction of n-butane, but no remarkable promoting effect was observed
[20].
The use of Pt-based modified SZ can avoid coke formation and
consequently enhance the stability [21], additionally, alumina modified
SZ showed better catalytic performance and simultaneously enhanced
stability at higher temperatures (>250 C) in the hydroisomerization of
◦

* Corresponding authors.
E-mail addresses: asifncp11@yahoo.com (A. Hayat), sohailncp@gmail.com (M. Sohail).

https://doi.org/10.1016/j.surfin.2021.101227
Received 28 March 2021; Received in revised form 9 May 2021; Accepted 17 May 2021
Available online 27 May 2021
2468-0230/© 2021 Elsevier B.V. All rights reserved.
I. Ullah et al.
n-butane. Hence, many research groups studied the alumina-supported
complex for n-butane isomerization [22–27], which suggested that the
loading of alumina by various methods can enhance the efficiency of
catalysts and stability in n-alkane isomerization reaction in the presence
of hydrogen. Pt was also investigated to be a well-modifying metal for
dehydrogenation and hydrogenation capability, therefore boosting up
the catalytic activity in an alkane isomerization reaction [21]. The
mechanical characteristics of SZ are poor, since the preparation of new
catalysts for n-butane isomerization is necessary to improve the catalytic
performance. The addition of Pt-Al into SZ could improve the mechan­
ical strength and stability.
In the recent research work, SZ, Pt/SZ, and PA/SZ were prepared by
a facile hydro-thermal route. The activity of all these prepared samples
was investigated and compared in the isomerization of n-butane.
Consequently, the main purpose of this work is to evaluate the better
catalyst among the prepared samples and to design a more stable cata­
lyst to improve the isomerization activity of n-butane.
2. Experimental part
2.1. Materials
ZrOCl2.8H2O (Zirconyl chloride octahydrate), aluminum nitrate
nonahydrate (Al(NO3)3⋅9H2O), Ammonia hydroxide (NH3.H2O, 30wt.
%), sulfuric acid (H2SO4, 98%, Aladdin) Alfa alumina (a-Al2O3 pellets),
chloroplatinic acid hexahydrate (H2PtCl6.6H2O), urea (Co(NH2)2), and
ethanol (C2H5OH), were purchased from the Aladdin Chemical reagent
company limited. All materials were used directly without further pu­
rification and treatment.
2.2. Preparation of catalysts
2.2.1. Preparation of SZ
Firstly, we prepared pure zirconia for the preparation of SZ. The
zirconia-alumina (Zr-Al) hydroxide was synthesized by mixing an
aqueous solution of ZrOCl2⋅8H2O (39.26 g) and Al(NO3)3⋅9H2O (3 g) in
300 mL deionized water under continuous aging at 600 rpm. Ammonia
hydroxide (26 wt. %) was introduced dropwise to the mixture till its pH
reached 10 and stirred overnight at 600 rpm. The precipitate was placed
in Teflon- lined autoclave at 150 C for 10 h in a hot vacuum oven. The
◦
Autoclave was chilled down to 30 C and the material was clarified,
◦
washed, and removed the chloride ions until its pH reached 8. The ex­
istence of chloride ion in the filtrate was identified by AgNO3 solution.
The bare zirconia-alumina hydroxide was dried in a hot air oven at 120
C for 24 h followed by calcination in air at 600 C for 4 h at the rate of
◦ ◦
1 C/min and labeled as Z. Then the desired extent of H2SO4 (sulfuric
◦
acid solution, 98%, Aladdin) was introduced drop wise to 1 g of bare
zirconia oxide. The solution was stirred (600 rpm) at room temperature
for 1 h, washed, clarified, and dried at 120 C for 24 h. Finally, calcined
◦
at 600 C for 4 h and labeled as SZ.
◦
2.2.2. Preparation of Pt/SZ
Pt-promoted SZ catalyst was synthesized via the incorporation of Pt
over the SZ by the incipient wetness method. The pre-treated sulfated
zirconia catalyst was placed in a beaker and introduced the desire
amount of Pt solution drop wise. The solution was agitated at ambient
temperature for 4 h, followed by drying at 120 C in a hot air oven for 24
◦
h and re-calcined at 650 C for 5 h. The obtained material was marked as
◦
Pt/SZ.
2.2.3. Preparation of Pt-Al2O3/SZ (PA/SZ)
Firstly, we prepared Pt- Al2O3 (PA) for the preparation of Pt-Al2O3/
SZ. The Pt-Al2O3 (PA) catalyst was synthesized by mixing α-Al2O3 and
H2PtCl6.6H2O. The desired amount of Pt solution was dissolved in 80 g
of deionized water (DIW), and 4 g of a-Al2O3 were added to a three-
necked round bottom flask under continuous stirring at 80 C. Then
◦
2
Surfaces and Interfaces 25 (2021) 101227
urea was introduced into the solution after 3 h. The subsequent solution
was stirred at 80 C for 8 h. The material was washed with C2H5OH and
◦
placed at 80 C in hot air own for overnight. Finally, calcined in a muffle
◦
furnace at 550 C for 5. Then the PA and sulfated zirconia was dissolved
◦
in 40 g of deionized water and agitated till a filtrate-free solution is
achieved. The solution was kept in an autoclave at 120 C for 8 h. The
◦
sample was washed and dried at 120 C and followed by re-calcination at
◦
550 C for 5 h. The obtained material was marked as PA/SZ.
◦
2.3. Characterization
XRD (X-ray diffraction) profiles for all catalysts were recorded with a
PANalytical X’Pert PRO diffractrometer over the range of angles of 2
theta = 5–50 , with CuKα (λ = 1.5405) monochromatized radiation
◦
activated at 30 mA of current and 40 kV of voltage, respectively. The
statistics were collected at a stage size of 0.1o and 10/min scan rate. The
Brunauer Emmett-Teller (BET) surface area, pore size distribution, and
volume of the pore, as well as the average size of the particle were
characterized via a micromeritics ASAP 2020 detector with N2
adsorption-desorption isotherm at liquid N2 temperature. The samples
were degassed at 300 ◦ C and 0.001 Pa for 16 h. FTIR (Fourier transform
infrared spectroscopy) was investigated using Nicolet 6700 FTIR tech­
nique to measure the connections between the hetero-metal oxide sys­
tems, the samples were prepared by using 0.5% KBr of the solid. The acid
strength of the catalysts was measured through temperature program
desorption (NH3-TPD) of ammonia using TPD/TPR chemisorption 5076
apparatus. The thermal behavior of samples were analyzed using TG 209
F1 (NETZSCH) TGA-DTA, the catalysts were heated from 100 to 800 C
◦
at a rate of 5 C/min to analyze the change in weight and TG curves.
◦
2.4. Catalytic activity evaluation
The n-butane isomerization over various catalysts was performed in
a fixed bed catalytic apparatus. A desire extent of granular catalyst (1 g,
0.30–0.45 mm) was retained in the center of the stainless-steel cylin­
drical apparatus and pretreated (at 300 C for 7 h) in the presence of
◦
hydrogen flow (300 mL/min) afore the isomerization reaction. After the
pretreatment of the catalyst, the conventional reaction parameters were
as follows: reaction temperature 180–260 C, WHSV weight hourly
◦
− 1
space velocity (WHSV) of 2 h , and n-butane was charged into the
reactor. A Shimadzu 2014 gas chromatograph fitted with SE30 capillary
column and FID (flame ionized detector) sensor was used to evaluate the
composition of feed and product. The evaluation indicators are as
follows;
Xi − Xf
%Xnb = × 100 (1)
Xi
Xn
%Sib = × 100 (2)
Xi − Xf
Xnb x Sib
%Yib = (3)
100
In Eqs. 1, 2, and 3, Xnb, Sib, and Yib is the conversion of n-butane,
selectivity to i-butane, and yield of i-butane respectively. Whereas Xi is
the mass of n-butane before reaction, Xf represents the mass of n-butane
after isomerization reaction, Xn is the mass of the individual product.
3. Results and discussion
3.1. XRD analysis
The XRD patterns [28,29] of SZ, Pt/SZ, and PA/SZ are presented in
Fig. 1, whereas all of the diffraction bands correspond to the monoclinic
and tetragonal zirconium. It has been observed that no bands are
attributed and related to the Pt, which suggests a maximum dispersal of
I. Ullah et al.
Fig. 1. XRD patterns of SZ, Pt/SZ, and PA/SZ samples.
Pt over SZ support. It has been analyzed that all the samples are in the
crystalline phase. The bands obtained at 2Ɵ are 28.54 , 28.45 , 35.35 ,
◦ ◦ ◦
and 46.27 representing the t-ZrO2 (tetragonal phase) of zirconia,
◦
however, the bands at 19.64 are consigned to the m-ZrO2 (monoclinic
◦
phase). The Pt-supported SZ samples indicating a high comparative
crystallinity. The monoclinic phase reduced in Pt/SZ and disappeared in
PA/SZ samples. This may be due to the fact that the loading of Pt and Al
has a positive influence on the monoclinic structure and leads to the
change of smaller parts of the monoclinic to the tetragonal phase, which
is thermally more steady, stable, and active for isomerization of
n-butane. These results revealed that both tetragonal and monoclinic
phase exists in the materials.
The crystallite sizes of catalysts were determined using the following
Scherrer equation.
Kλ
D= (i)
βCOSθ
Where, “D” represents the size, K is shaping constant, “λ” is wave­
length radiation, “β” is the radian of line and “θ” is angle of Bragg.
3.2. N2 Adsorption/desorption
The BET surface area and pore size distribution [30–32] of SZ, Pt/SZ,
and PA/SZ materials were carried out through BET (Brunauer-
Fig. 2. (a) Nitrogen adsorption-desorption isotherm and (b) pore size Distribution.
3
Surfaces and Interfaces 25 (2021) 101227
Emmett-Teller) in the presence of N2 adsorption-desorption isotherm.
The nitrogen adsorption/adsorption isotherms, pore-volume, and pore
diameter distributions of the SZ, Pt/SZ, and PA/SZ catalysts are illus­
trated in Fig.2a-b. The BET surface area, volume of the pore, and average
sizes of pore are presented in Table.1. It can be observed clearly that all
of the catalysts shown the type H3 (hysteresis loops), which has been
related with the vessel condensation proceeding in the mesoporous,
suggesting the presence of mesoporous arrangement in the samples
[33–36]. Most prominently, the loop of hysteresis shifted to a
high-pressure area in PA/SZ sample as compared to SZ and Pt/SZ,
signifying that the mesoporous structure was altered. The BET surface
area of PA/SZ was higher in comparison with SZ and Pt/SZ, besides a
greater volume of pore and smaller average pore size, which is in
agreement with previous literature [37]. Furthermore, several re­
searchers have been suggested that the presence of alumina leads to the
improvement of the specific surface area [38,39], and here, the mixing
of Pt/Al2O3 (PA) with SZ shows a broad effect than the other samples. It
can be seen from Fig.2a that PA/SZ has the smallest distribution of pore
size among all of the prepared catalysts. In Table.1 it has been also
determined that the Pt/SZ has the highest average pore size, it confirms
that some mesoporous alumina also is present over the surface of SZ.
3.3. FTIR analysis
The FTIR spectra [40,41] of SZ, Pt-promoted SZ, and Pt-Al promoted
SZ samples were analyzed in the collection of 400–500 cm− 1 as dis­
played in Fig.3. The samples prepared via the hydrothermal method
corresponds to the formation of Zr-O-Zr bonds, which was confirmed by
the bands in the range of 873–716 cm− 1 [42]. A light band about 3441
cm− 1 is consigned to physically adsorbed water, while the band around
1643 cm− 1 is attributed to the H-O-H (bending type) bond of corre­
sponding H2O [43]. The peak at 1322 cm− 1 was related to the Zr-O-H
bond (bending vibration) [44]. The band approximately at 3180 cm− 1
in sulfated zirconia, the intensity of O-H (stretching vibration) bond
reduced owing to the attraction between hydrogen bond. This may be
due to the presence of SO−4 2 in sulfated zirconia [45, 46].
3.4. NH3-TPD
The acidity and concentration of the samples were characterized by
the desorption of ammonia through temperature-programmed desorp­
tion (NH3-TPD). The pretreatment of materials was performed under
helium (He) flow at 600 C for 1.5 h to remove water and the gas
◦
adsorbed by samples, followed by cooling to ambient temperature. Then
nitrogen gas was passed through samples, and the substantially adsor­
bed ammonia was eliminated by flowing He gas 2 h at 100 C. The NH3-
◦
I. Ullah et al. Surfaces and Interfaces 25 (2021) 101227

Table. 1
Characteristics and surface properties of selected samples.
Sample SBET (m2/g) Vpore (cm3/) Dpore (nm) Pas (nm) TA (mmol/g) S (wt.%) Crystallinity (Ao)

SZ 142.854 0.339 7.132 23.634 0.214 1.78 163

0.6%Pt/SZ 147.654 0.295 6.803 24.361 0.409 2.43 165
PA/SZ 152.276 0.386 7.168 21.453 0.648 2. 57 168

3.5. TGA (Thermogravimetric analysis)

The TGA of SZ, Pt/SZ, and PA/SZ are shown in Fig.5. The TG curves
of SZ represent that the first weight loss at 100 C is associated with the
◦

removal of substantially adsorbed water over the surface, while the

second weight loss 260-400 C is owing to the elimination of water
◦

molecules from the surface [48]. The weight loss between 450-800 C
◦

has corresponded to the decomposition of sulfur species. The Pt/SZ and

PA/SZ samples indicate an almost similar trend which is due to the low
content of Pt in both samples. The whole TG profile shows 6% weight
loss of sulfate species from the SZ sample. The results revealed the suf­
ficient stability of the synthesized samples up to 800 C.
◦

3.6. Activity evaluation

3.6.1. Effect of different catalysts

The PA/SZ, Pt/SZ, and SZ catalysts were applied for n-butane
isomerization reaction in a fixed bed catalytic reactor at 220 C. The
◦

Fig. 3. FTIR spectra of SZ, Pt/SZ, and PA/SZ samples. influence of these catalysts on the catalytic activity of straight-chain
butane isomerization was investigated as presented in Fig.6. It can be
TPD curves were recorded from 100 to 600 C at a rate of 10 C/min, seen that PA/SZ sample has a significant effect on isomerization of n-
◦ ◦

which are presented in Fig.4. Two bands ensued for all materials, at­
tributes to desorption of NH3 on weak, and strong acidic positions
respectively. In PA/SZ sample the peaks for weak, strong and weak acid
sites moved from 219 C to 221 C and 400 C to 424 C respectively. It
◦ ◦ ◦ ◦
butane. The conversion of n-butane, selectivity, and yield of i-butane is
higher than that over Pt/SZ and SZ samples. Moreover, it is surprising to
see that the selectivity and yield to isobutane are increased dramatically
over PA/SZ samples. This might be due to the fact that PA/SZ is well

was reported that the significance of surface hydroxyl group (OH) and
sulfate species on the development of acid positions for SZ. It was also
stated that the weak and strong acid centers were formed by two sulfate
species. Simultaneously, the acid strength also increased for both weak
and strong acidity. The weak and strong acid positions were detected in
all samples. Even at high-temperature zone the curves result owing to
the disintegration of sulfate ions [47].
crystalline in-phase and Pt is highly dispersed on an alumina support.
Another possible reason might be that Pt and Al loading to rises the
extent of sulfur retention on the surface of SZ which then stimulates the
oxidative dehydrogenation to n-butane and the skeletal isomerization.
These results revealed that the incorporation of PA into sulfated zirconia
sample broadly effects the catalytic activity of n-butane isomerization
(Table.2).

3.6.2. Influence of reaction temperature

The influence of reaction temperature over the catalytic performance
of n-C4 isomerization was investigated from 180–260 C under constant
◦

Fig. 4. NH3-TPD profiles of SZ, Pt/SZ, and PA/SZ. Fig. 5. TGA curve of (a) SZ, (b) Pt/SZ, and (c) PA/SZ catalysts.

4
I. Ullah et al. Surfaces and Interfaces 25 (2021) 101227

higher temperature selectivity to cracking products governs. As illus­

trated in Fig.7, the i-butane selectivity reduces greatly at high temper­
atures. The possible reason for this is that it high temperatures cracking
and disproportion reaction takes place. The optimum reaction temper­
ature was 220oC, because at this temperature the selectivity to i-butane,
conversion of n-butane, and yield of i-butane butane were 98.96%,
71.04%, and 70.30% (wt. %) respectively (Table.3).

3.6.3. Stability test of catalysts

The conversion of n-butane in the isomerization reaction over
different catalysts at 220 C depends on the reaction time on stream
◦

which is presented in Fig.8. It could be seen clearly that the reaction

Fig. 6. Conversion, Selectivity, and Yield of i-butane isomerization over PA/SZ,
Pt/SZ, and SZ catalysts.
strained a stable phase at 25 h of reaction time on stream over the three
samples, however, Pt/SZ and SZ deactivated slightly or sharply at the
early stage of the reaction. For Pt/SZ, the conversion reduced signifi­
cantly within 8 h. On the other hand, Pt/SZ showed insignificant
deactivation, sufficiently excellent stability, indicating that Pt dispersed
well in the sulfated zirconia and enhanced the catalytic stability.
Furthermore, the conversion of n-butane for SZ catalyst decreased
dramatically to the lowest steady-state value within 12 h, whereas its
initial activity was slightly higher than other samples. The reason for
this could be the loss of sulfate ions and change in the oxidation phase of
sulfur.

Table. 2 4. Conclusion
Influence of various catalysts over reaction performance of n-butane
isomerization.
A series of SZ-based catalysts were successfully prepared by a facile
Catalysts % Conversion % Selectivity % Yield hydro-thermal process. In this research, the catalytic performance of SZ,
SZ 47.73 85.86 40.98 Pt promoted SZ, and Pt-alumina promoted SZ samples were investigated
Pt/SZ 59.58 90.72 54.05 in n-butane isomerization. It was investigated that Pt/Al2O3 promoted
PA/SZ 71.04 98.96 70.30 sulfated zirconia has higher selectivity to i-butane, the yield of i-butane,
and conversion of n-butane compared to that of Pt/SZ and bare SZ. The
pressure (1 atm) and WHSV (2 h− 1), as shown in Fig.7. The reaction was Pt/Al2O3 that is introduced into sulfated zirconia by hydrothermal
performed in the existence of PA/SZ at 10 h for each temperature. It was method is capable to enhance the content and acidic strength, which is
noticed that with raising the temperature, the reaction rate of n-butane an indicator to well equilibrium between metal part and acid site in the
isomerization first increased gradually, while decreases with further bifunctional catalyst and consequently stimulate the catalytic perfor­
increase in temperature. These findings revealed that the rise in reaction mance. PA/SZ catalyst was demonstrated to be extremely efficient in the
temperature up to 220 C speed up the activation energy of n-butane
◦
n-butane isomerization reaction, giving a remarkably high selectivity to
which in turn increasing the conversion of n-C4 and yield of isobutane. i-butane (98.96%), yield of i-butane (70.30%), and conversion of n-
Furthermore, the rise of reaction temperature should also initiate the butane (71.04%) at a temperature of 220 oC and 2 h− 1 (WHSV).
cracking reaction of n-butane and diminish the selectivity to i-butane. At Furthermore, it was observed that the reaction reached a stable phase at
low temperature, selectivity toward iso-butane was high, however, at 25 h of time on stream for all the synthesized samples. PA/SZ showed
higher catalytic stability among others catalysts. Meanwhile, it is
essential to explore and gain an in-depth insight into the related cata­
lytic mechanism, which is under our consideration and future study
focus. Finally, we are convinced that the recent research work could
convey new prospects to improve the isomerization performance of n-
butane and may leads to open the door in preparation and character­
ization of bifunctional catalysis in the presence of noble metal.

Author’s statement

Journal of surface and interface

It is a special letter for you that the paper “Platinum-Alumina

Table. 3
Influence of various reaction temperatures over reaction performance of n-
butane isomerization.
Temperature % Conversion % Selectivity % Yield

180 50.65 91.05 46.12

200 62.38 95.99 59.87
220 71.04 98.96 70.30
240 65.74 90.27 59.34
260 58.83 78.50 46.18
Fig. 7. The relation between reaction temperature and catalytic activity of
280 53.18 74.31 39.51
n-butane.

5
I. Ullah et al.
Fig. 8. n-butane conversion over PA/SZ, Pt/SZ, and SZ samples as a function of
reaction time on stream.
Modified SO42–ZrO2/Al2O3 Based Bifunctional Catalyst for signifi­
cantly improved n-butane isomerization performance” had been revised
and submitted R1 to the Journal of Surfaces and Interfaces (Manuscript
Number: SURFIN-D-21-00707).
The initial submission of paper not contain my main supervisor, co-
supervisor and the authors that help me in my paper. I am going to
describe them one by one.
1. Ikram Ullah, T.A. Tah, Asma M. Alenad done experiments, pur­
chase chemicals, done some important characterizations and write
and design paper. Dr.sohail collaborated whole data and give a paper
design.
2. Muhammad sohail, Arkom Palamanit and Ahmad Irfan is my su­
pervisor and co-supervisor team in manuscript. They helped me in
perform experiments, English editing, polishing from irrelevant
words, bestow suggestion and design paper in aligned format that are
conscript in co-authors list. I obey my co-supervisor words.
3. Professor Javid Khan, Ikram Uddin and Ashiq Hayat provide
special arrangement for the cost on characterizations such as XPS,
XRD, FTIR, SEM, NMR, EPR, BET and CO2 reduction expenses. The
funds are available.
So the above explanation is only the justification that please accept
the author list and hope will be fit for acceptance. All the authors, co-
authors and corresponding authors does not show any conflict of in­
terest and for more verification, their original emails are enlisted in the
main system. Journal can further justify this. We hope that you find our
responses satisfactory. On level of corresponding coauthor, all authors
have no any conflict of interest.
As always, thank you very much for your time and consideration.
Regard
Dr. Asif Hayat Asifncp11@yahoo.com
Declaration of Competing Interest
All the authors and co-authors enlisted in the given manuscript show
no any conflict of interest.
Thank you
Acknowledgment
This work is financially supported by the National Basic Research
Program of China (2013CB632405 and 2014CB260406), the National
6
Surfaces and Interfaces 25 (2021) 101227
Natural Science Foundation of China (21425309 and 21173043), the
State Key Laboratory of NBC Protection for Civilian (SKLNBC2013-04
K),and the Specialized Research Fund for the Doctoral Program of
Higher Education (20133514110003).
The authors extend their appreciation to the Deanship of Scientific
Research at King Khalid University (KKU), Saudi Arabia for funding
through research groups program under grant number R.G.P.2/28/42.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.surfin.2021.101227.
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