A Simple but Efficient Catalytic Approach for the Degradation of Pollutants in Aqueous Media through Cicer arietinum Supported Ni Nanoparticles

Article abstract of DOI:10.1515/zpch-2018-1297

Plant based materials are considered to have broad applications in the remediation of toxic materials. In this report, we present an environmental friendly and economic Cicer arietinum, named as (CP) supported for the synthesis of Ni nanoparticles (NPs) designated as Ni@CP. The in situ Ni@CP NPs were obtained using aqueous medium in the presence of sodium borohydride (NaBH4) as a reducing agent. The prepared catalysts were applied for the hydrogenation/degradation of p-nitrophenol (PNP), o-nitrophenol (ONP), and 2,4-dinitrophenol (DNP), as well as congo red (CR), methyl orange (MO), methylene blue (MB) and rhodamine B (RB) dyes. The amount of total metal ions adsorbed onto the CP was evaluated by flame atomic absorption spectroscopy. The Ni@CP catalyst was characterized through PXRD, FTIR, FESEM and EDX analyses.

Full text of DOI:10.1515/zpch-2018-1297

Z. Phys. Chem. 2019; aop
Shahid Ali Khan*, Shagufta Rasool, Khaliq Ur Rahman,
Shah Hussain, Inamullah Khan, Muhammad Ismail,
Aliya Farooq, Sarzamin Khan, Mian Ahmad Raza,
Abdullah Muhammad Asiri and Sher Bahadar Khan*
A Simple but Eflcient Catalytic Approach for the
Degradation of Pollutants in Aqueous Media
through Cicer arietinum Supported Ni
Nanoparticles
https://doi.org/10.1515/zpch-2018-1297
Received September 5, 2018; accepted August 12, 2019
Abstract: Plant based materials are considered to have broad applications in
the remediation of toxic materials. In this report, we present an environmental
friendly and economic Cicer arietinum, named as (CP) supported for the synthe-
sis of Ni nanoparticles (NPs) designated as Ni@CP. The in situ Ni@CP NPs were
obtained using aqueous medium in the presence of sodium borohydride (NaBH4)
*Corresponding authors: Shahid Ali Khan, Department of Chemistry, University of Swabi,
Anbar-23561, Khyber Pakhtunkhwa, Pakistan; Center of Excellence for Advanced Materials
Research (CEAMR), King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia;
and Department of Chemistry, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi
Arabia, e-mail: shahidsawal007@gmail.com; and Sher Bahadar Khan, Center of Excellence
for Advanced Materials Research (CEAMR), King Abdulaziz University, P.O. Box 80203, Jeddah
21589, Saudi Arabia; and Department of Chemistry, King Abdulaziz University, P.O. Box 80203,
Jeddah 21589, Saudi Arabia, e-mail: sbkhan@kau.edu.sa
Shagufta Rasool: Department of Chemistry, Sarhad University of Science and Technology,
Peshawar, Pakistan
Khaliq Ur Rahman, Inamullah Khan and Sarzamin Khan: Department of Chemistry, University
of Swabi, Anbar-23561, Khyber Pakhtunkhwa, Pakistan
Shah Hussain: Department of Chemistry, Govt. Postgraduate College, Nowshera-24100,
Khyber-Pakhtunkhwa, Pakistan; and Department of Chemistry, Abdul Wali Khan University,
Mardan 23200, Pakistan
Muhammad Ismail: Department of Chemistry, Kohat University of Science and Technology,
Kohat, Pakistan
Aliya Farooq: Department of Chemistry, Shaheed Benazir Bhutto Women University, Peshawar,
Pakistan
Mian Ahmad Raza: Department of Agriculture (Plant Breeding and Genetics), University of
Swabi, Swabi, Khyber Pakhtunkhwa
Abdullah Muhammad Asiri: Center of Excellence for Advanced Materials Research (CEAMR),
King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia; and Department of
Chemistry, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

2
| S. A. Khan et al.
as a reducing agent. The prepared catalysts were applied for the hydrogenation/
degradation of p-nitrophenol (PNP), o-nitrophenol (ONP), and 2,4-dinitrophenol
(DNP), as well as congo red (CR), methyl orange (MO), methylene blue (MB) and
rhodamine B (RB) dyes. The amount of total metal ions adsorbed onto the CP
was evaluated by flame atomic absorption spectroscopy. The Ni@CP catalyst was
characterized through PXRD, FTIR, FESEM and EDX analyses.
Keywords: Cicer arietinum; dyes degradation; environmental pollution; Ni@CP;
nitrophenols.
1 Introduction
The applications of nanoscale materials have been arose in the scientific commu-
nity because of it distinguishing characteristics including high surface area to vol-
ume ratio as compared to their bulk counterparts [1–3]. The large surface/volume
ratio provides new chemical, physical, mechanical, magnetic, and optical fea-
tures to the catalyst. Recently, Metal nanoparticles (MNPs) has become an emerg-
ing and important field at industrial level. MNPs can be synthesized through
non-biological methods i.e. physically or chemically. Non-biological fabrication
involves organic solvents and other reducing agents to support and stabilize the
NPs [4]. The Physical methods involves ball milling, spray pyrolysis, plasma arc-
ing, ultra-thin films, thermal evaporate, lithographic techniques, pulsed laser
desorption, sputter deposition, diffusion flame, and molecular beam epitaxy [5].
Sol–gel process, electrode position, chemical vapor deposition, chemical solution
deposition, Langmuir Blodgett method, soft chemical method, catalytic route,
hydrolysis, wet chemical method and co-precipitation are included in the chemi-
cal methods [5, 6]. However, environmental issues are associated with these non-
biological process and therefore limits its vast applications. Therefore, there is an
urgent need to remove these recent existing methods due to their non ecofriendly
nature. A number of approaches have been present in the literature for the reac-
tion [7–12], but still much efforts and novel protocol are required that not only
stabilize, but also are ecofriendly. Plant based NPs are considered as the best
candidate because it stabilized the NPs by their inherent biological components
[13]. However, the nanosize MNPs aggregated readily due to their high surface
energy, small size and van der Waal forces. Thus the aggregation of NPs results in
decreasing their catalytic activity and reusability. Therefore, a systems are needed
to increase NPs stabilization and avoid aggregation [14–16].
In order to prevent aggregation of NPs it is mostly supported on synthetic and
natural polymeric materials. Natural polymers used are mostly starch, chitosan,
chitin and cellulose as support for NPs. As a compared to the conventional
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

A Simple but Eflcient Catalytic Approach
| 3
adsorbents, plants supported materials gained much interest due their plentiful
existence, non-toxic nature, high-efficiency, low-cost, as well as environmental
friendly nature [17–19]. It has been found that biocompatibility, natural abun-
dance, hydrophilicity, and biodegradability of plants based materials make them
distinct from the other conventional adsorbent. Besides, MNPs exhibit a broad
antimicrobial spectrum [17, 20].
In wastewaters large numbers of organic substances are present as pollutants
that are discharged from normal households and industrial sectors. These organic
pollutants can be found in surface as well as in ground water wells. A num-
ber of aromatic compounds, especially organic carcinogenic dyes which causes
cancer, nephritis, and malformation and many other diseases are reported [21–
23]. The color effluents from these industries not only causes the water surface
to become colored, but also becoming the sources of environmental damage for
living organisms by decreasing the water re-oxygenation capacity and blocking
sunlight, thus, causing an interruption in the aquatic life. Besides these injurious
substances along with nitrophenols and dyes passes to the drinking water, which
causes damage to human [24, 25]. For the removal of these injurious substances
from the effluents, we use Cicer arietinum as a supportive materials.
Cicer arietinum or chick pea is a legume of the family fabaceae and sub fam-
ily faboideae, and are known as gram or garbanzo bean. Sometime they are still
brewed as an alternative to coffee. In South Asia, Bengal, grams and chickpeas are
used to make curries and some of the most popular vegetarian foods in Diaspora
community of various countries served with steamed rice or breads [26]. In Indian
cuisine popular dishes made with chickpeas flour include such as mirapakaya
mirchi bada. The unripe chickpeas leaves are eaten as food vegetable salad and
as a raw snack [27].
In the present study, we used Cicer arietinum fruit powder as a supported
materials for the stabilization of Ni NPs for the environmental remediation of
organic dyes and nitrophenols.
2 Experimental
2.1 Materials
Chemicals such as ortho nitrophenol (ONP), meta nitrophenol (MNP), para nitro-
phenol (PNP) and 2,4-dinitrophenol (DNP), Methyl orange (MO), Congo red (CR),
and Rhodamine B (RB) were purchased from Sigma Aldrich, Darmstadt, Ger-
many. Sodium borohydride (NaBH4), nickel nitrate hexahydrate (Ni(NO3)2·6H2O)
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

4
|
S. A. Khan et al.
and methylene blue (MB) were purchased from Daejung chemicals South Korea.,
Germany. Cicer arietinum were purchased from the local market District Kohat.
2.2 Preparation of Ni NPs
Chick pea supported metal nanoparticles were prepared by two steps method.
Firstly, chick pea were blended by electric blender. Then prepared 0.2 M con-
centration solutions of nickel salts by using nickel nitrate hexahydrate in dis-
tilled water. Then dipped about 1 g of the CP powder into 50 mL solution of
(Ni(NO3)2·6H2O) for overnight for the complete saturation of adsorption sites. The
color of the CP powder changed after the adsorption of Ni+2. The change in color
of the material was due to the adsorption of Ni2+ ions. The adsorption ability of
the C. arietinum was measured by using atomic absorption spectrophotometer.
In the second step, the dipped powder was collected using filter paper and
dried at room temperature. For the Ni Nps synthesis, 10 mg of treated Ni+2 C. ari-
etinum powdered was treated with 0.5 mL of freshly prepared 1 M sodium borohy-
dride solution, where the color of the powder turned black. The prepared catalyst
was dried and used for further experiments.
2.3 Catalytic reduction reactions
After preparation, the synthesized catalyst was used for the reductive hydrogena-
tion of nitrophenols as well as for the degradation of MO, CR, MB, and RB dyes.
For nitrophenols reduction an aqueous solution of 0.1 mM was prepared in double
distalled water. For the reaction vessel UV cuvette was used. 2.5 mL of the pre-
pared nitrophenols solution was put in a UV cuvette and recorded their spectra
in a time-dependent UV-Vis spectrophotometer. After that, 0.5 mL of freshly pre-
pared NaBH4 solution was added as a result a change in color was recorded for
nitrophenols from dim yellow to sharp yellow color with increase in wavelength.
After that, 10 mg of catalyst was added to the reaction vessel. The reduction reac-
tions was initiated after the addition of catalyst and a gradual decrease in the
nitrophenols concentration was observed. Consequently, the regular decrease in
their λmax with time after addition of catalyst was monitored.
Similarly, for the dyes reduction, 10 mg of the Ni@CP catalyst was employed
against the degradation of CR, MO, MB and RB dyes (0.05 mM). Likewise, 2.5 mL
solution was put in a UV cuvette and then treated with 0.5 mL of freshly prepared
solution of NaBH4 and recorded their spectra with time. To the same reaction
vessels 10 mg of the catalyst was added.
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

A Simple but Eflcient Catalytic Approach
| 5
The following formula was used for the decrease in the original concentration
of the analyte
Decrease in concentration = Ct/Co
where, Ct is the final concentration of analyte and Co is their original
concentration.
The extent of reduction/degradation was confirmed from the following for-
mula
Ct
Co
% reduction/degradation = Co −
× 100
where Ct is the final concentration and Co is the initial concentration of the
analyte.
2.4 Instrumentation
Cu Kα radiations λ = 0.154 nm (Thermo scientific diffractometer, Waltham, MA,
USA) XRD spectrum was used for the peak crystallinity of Ni NPs. The XRD spec-
trum was recorded from 2θ = 10–80°. The morphology like shape and particle
size of Ni@Cp was determined by Field Emission-Scanning Electron Microscope
(FESEM) JEOL (JSM-7600F, Tokyo, Japan). Similarly, the interaction of NPs with
the inherent functional group of C. arietinum and the functional group anal-
ysis of C. arietinum were investigated through ATR-FTIR spectroscopy (nicolet
is50 ATR-FTIR spectrometer Thermo scientific, Waltham, MA, USA). The different
batch experiment of nitrophenols and dyes degradation were performed in the
time dependent UV–visible spectrophotometer (Shimadzu, MultiSpec1501, Tokyo,
Japan). The C. arietinum uptake capacity of the Ni+2 ions was studied through
flame atomic absorption spectrophotometer FAAS, Perkin Elimer 400 (Waltham,
MA, USA).
3 Results and discussion
3.1 Atomic absorption studies of catalyst
The adsorbtion of Ni+2 on powder of CP was evaluated by the decrease in the con-
centration of Ni salt solution. The percent uptake of the Ni+2 was calculated using
the following equation.
(Cs − Ct) × 100
Percent metal ions uptake (Pa) =
Cs
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

6
|
S. A. Khan et al.
where Cs is the concentration of stock solution (mg/L) and Ct is the concentration
of solution after treatment with powder of CP for 5 h. The uptake capacity of Ni2+
ions were found 22.5%.
3.2 Structural characterization
3.2.1 FESEM
The Morphology of the finely powdered Ni@CP was scrutinized through FESEM.
The FESEM micrograph were taken at low and high magnification as shown in
Figure 1a–d. The left side micrograph is at low magnification whereas the right
one is at high magnification. At low magnification oval shaped spheres are indi-
cated, however, at higher magnification Ni NPs were clearly seen in Ni@CP micro-
graph (Figure 1d), no such particles appeared in the remaining 3 images 1a–c. At
high resolution the CP become melted due to the impact of high energy electrons
Fig. 1: FESEM images on the left side is at low resolution 10 µm and at right side high res-
olution micrograph 100 nm, FESEM images of powder of Cicer arietinum (a,b) and Ni@CP
(c,d).
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

A Simple but Eflcient Catalytic Approach
| 7
beam, as shown in Figure 1b and d. The high resolution FESEM images shows
that the Ni nanoparticles are strongly intact in the CP sample where it is almost
homogenously dispersed and exhibited as a bright white spot (Figure 1d).
3.2.2 EDS
The energy dispersive spectroscopy is one of the most authentic and reliable tech-
nique for the determination of elemental analysis in a mixture and confirmed the
purity of a sample. The EDS spectrum was plotted as binding energy in KeV vs.
Counts/s. The counts/s is the radiations which are passes from the detectors in
1 s. An area was selected from the FESEM plot of Ni@Cp (Figure 2a), as a result
an elemental window appeared (Figure 2b). The elemental window indicated C
on the energy scale at 0.3 KeV, O 0.5 KeV and Ni 1.0 KeV. It is clear that the car-
bon is present 71.03 by weight% which is followed by oxygen (21.6%) and Ni 7.36
weight%, respectively. The high content of carbon in the sample is true due to the
organic nature of the CP.
3.2.3 XRD
The XRD spectrum is indicated in the inset of Figure 3a. A small peak displayed at
2θ = 44.1° indicating the crystalline Ni Nps. The less sharp peak for Ni NPs was
due to the poor growth of crystalline NPs during the synthesis. A sharp amorphous
hump appeared at 2θ = 27.8° indicated the amorphous nature of C. arietinum
(Figure 3a).
Fig. 2: Area selection from FESEM plot (a) and elemental analysis window indicating weight%
(b) of Ni@CP nanoparticles.
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

8
|
S. A. Khan et al.
Fig. 3: PXRD spectrum of Ni NPs (a) and FTIR spectrum of the powder of CP and CP based Ni
NPs (b).
3.2.4 FTIR
The functional group was confirmed from ATR-FTIR. The absorbance at
3389 cm−1 was showing the –OH stretching vibration in Ni@CP while same
vibration was appeared at 3286 cm−1 for C. arietinum. The reason for the higher
value of –OH stretching vibration in Ni@CP is due to the multiple H-bonding.
The –OH bending was appeared at 1650 cm−1. The C–H single bond asymmet-
ric vibration exhibited in most of the organic compounds in the range of 2853–
2960 cm−1, therefore, these two peaks at 2853 and 2929 cm−1 are due to the asym-
metric stretching vibration of C–H single bond. The C–O stretching appeared at
1018 cm−1 in both NPs and C. arietinum (Figure 3b).
3.3 Catalytic study for the reduction of nitrophenols
Primarily, 10 mg of powder of CP was tested against 3 mL of 0.1 mM PNP and
0.05 mM MO dyes in order to explore its adsorption/degradation capacity, but we
have found no adsorption/degradation phenomenon in both cases. The modified
CP sample (Ni+2 adsorption on CP) and C. arietinum was treated with 1 mL of 1 M
NaBH4 solution which become black in color and unaffected, respectively. The
black color of modified CP sample confirming the formation of metallic Ni NPs
onto the CP sample. These data reflects, that Ni adsorption on CP is responsible for
the NPs formation, powder of CP itself have no role in NPs formation, although CP
served as an efficient support for the Ni NPs by avoiding it from the agglomeration
and aggregation.
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

A Simple but Eflcient Catalytic Approach
| 9
We make different experiments in order to explore the in-depth picture of
these materials. We observed that there is no inherent materials or substance in
the C. arietinum which are responsible for the degradation of pollutants. After
that, we added 0.5 mL NaBH4 to the PNP and MO, where PNP is converted to its
phenolate anions and MO dye is converted to its hydrazine derivatives. After a pro-
long time the NaBH4 itself does not brought a noticeable change in the reduction
of PNP and MO. The addition of NaBH4 is a thermodynamically favorable pro-
cess, but not kinetically. The NaBH4 itself not sufficient to cross the activation
energy barrier required for the reduction of PNP and MO. However, along with
NaBH4 Ni@CP degraded the PNP and MO dyes. We can say that both Ni NPs and
NaBH4 are the prerequisite for this reduction reaction. The Ni@CP degraded the
phenolate anion of PNP and hydrazine derivative of MO.
3.3.1 Nitrophenols reduction
Four different nitrophenols ONP, MNP, PNP and DNP were selected as a model pol-
lutants. The pure ONP, MNP, PNP and DNP have λmax at 351, 332, 318 and 352 nm,
respectively. However, by the addition of NaBH4 the increase in wavelength (red
shift) occurred and the corresponding nitrophenols are converted to their phe-
noalte anions. The phenolate anions are at higher wavelength as compared to
their pure phenols [28]. For instant, the phenolate anions of ONP, MNP, PNP and
DNP appeared at λmax 420, 393, 400 and 430 nm, respectively. After the addition
of Ni@CP the decrease in the original concentration of the respective phenolate
anions was observed and their respective nitroamine appeared with the reaction
proceedings. The reduction of ONP, MNP, PNP and DNP was completed in 16, 12, 13
and 34 min. The 4-NP results was compared with the literature [29]. However, after
applying the Ct/Co kinetics the fastest reduction was observed for PNP. The MNP
are faster initially, but gradually decrease, while a smooth trends in the reduc-
tion of ONP and DNP was observed as shown in the inset of Figure 4a–d. See
Supplementary information S-1 for the UV-Vis spectrum of MNP.
3.3.2 Dyes reduction
Ten milligram of the Ni@CP was used for the degradation of 0.05 mmol of two azo
dyes (CR, MO) and two cationic dyes (MB, RB). The CR appeared at λmax 500 nm
and MO at λmax 464 nm as shown in the inset of Figure 5a,b. The CR dye has two
azo bonds and MO have one, therefore, the CR appeared at higher λmax then MO
due to extended conjugation as indicated in the UV-vis chromatogram. The point
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

10
|
S. A. Khan et al.
Fig. 4: Time-dependent UV-vis spectrum for the reduction of ONP (a), PNP (b), DNP (c) the
labelled a in the spectrum a–c indicating the phenolate ion after the addition of NaBH4, while
labelled b in the spectrum a, and b indicating the amine counter part of the respective nitro-
phenols. The kinetic data derived from Ct/Co suggesting the strongest reduction rate of PNP
as compared to other nitrophenols (d). See Supplementary information S-1 for the UV-Vis
spectrum of MNP.
Experimental condition: The concentration of the ONP, MNP and DNP was 0.5 mM and the
concentration of PNP was 0.1 mM. Ten milligram of the catalyst was used.
a, in 4a indicated the peak of pure 0.05 mmol CR dye and the point b showing
the hydrazine derivative of CR which is formed after the addition of NaBH4. Simi-
larly, the same procedure was emplyeed for the removal of MO and cationic dyes
MB and RB which appeared at λmax 464, λmax 664 and λmax 554 nm, respectively
as shown in Figure 5b–c. However, with the addition of NaBH4 the MB and RB
are converted to the luco form. The point a and b in graph 4c and 4d indicating
the pure dye peak and its luco derivatives, which was formed after the addition of
NaBH4. After that, 10 mg of the Ni@CP was used against the removal of all dyes.
The kinetic was determined through Ct/Co where the rate of degradation was in
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

A Simple but Eflcient Catalytic Approach
| 11
Fig. 5: Time-dependent UV-vis spectrum for the degradation of CR (a), MO (b), MB (c) and RB
(d), the point a and point b in the spectrum a-d indicating the pure dye without NaBH4 and
with NaBH4 respectively. The kinetic data revealed Ct/Co (e) and % reduction (f) showing the
strongest activity of Ni@CP against MB.
Experimental condition: The concentration of all the dyes were 0.05 mM and catalytic amount
was 10 mg.
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

12
| S. A. Khan et al.
the order MB > RB > MO > CR (Figure 5e). Same kinetics rate trends was observed
in the % degradation of all dyes (Figure 5f).
3.3.3 Simultaneous reduction of dyes and PNP
The simultaneous reduction of RB-MB, PNP-CR and MO-MB were degraded by
using Ni@CP. The simultaneous reduction is extremely important for the indus-
trial point of view, where multiple pollutants are coexisted. 2.5 mL of RB and
2.5 mL of MB were mixed together and then 0.5 mL of 1 M NaBH4 was added. From
this solution 3 mL of the mixture were taken in a UV cuvette and 10 mg of the cat-
alyst was added. The UV-Vis spectrum were recorded with the proceeding of the
reaction as a function of time (Figure 6a). Figure 6a displayed a small window,
indicating the mixing of RB and MB. From the λmax it is clear that no chemical
reactions was occurred between the mixing of the two dyes. After that NaBH4 was
added as indicated in the main window of Figure 6a. By the addition of Ni@CP the
RB and MB started degradation, where MB degraded faster as compared to RB.
Fig. 6: Time-dependent UV-vis spectrum for the degradation of mixed system of RB-MB in
17 min (a) PNP-CR 9 min (b) MO-MB 6 min (c). Small spectrum in each inclusion from a–c
indicating the peak of pure sample.
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

A Simple but Eflcient Catalytic Approach
| 13
The whole mixture took 17 min for the complete degradation (Figure 6a). Simi-
lar experiments were performed for the complete degradation of PNP-CR in 9 min
(Figure 6b) and MO-MB in 6 min (Figure 6c).
4 Conclusion
In this study we report the green and facile synthesis of CP based Ni NPs. The
adsorption ability of the chick pea fruit powder were determined by using atomic
absorption spectrophotometer. The prepared Ni@CP were morphologically and
structurally characterized by using PXRD, FESEM, and EDS and FTIR. The Ni@CP
exhibit excellent activity in the reduction of carcinogenic/toxic azo and cationic
dyes as well as different nitrophenols. The prepared Ni@CP NPs can be prepared
on large scale, and can be used for the remediation of toxic dyes and nitrophenols
for purification of natural water.
Acknowledgment: The authors highly acknowledged the Higher Education
Commission (HEC) of Pakistan for providing Fund for the project No. 21-1942/
SRGP/R&D//HEC/2018.
Conflict of interest: The content of this manuscript has no conflict of interest and
all the authors have approved.
Statement of human and animal rights: This article does not contain any studies
with human or animal subjects performed by the any of the authors.
References
1. A. Albanese, P. S. Tang, W. C. Chan, Ann. Rev. Biomed. Eng. 14 (2012) 1.
2. V. S. Raghuwanshi, R. Wendt, M. O’Neill, M. Ochmann, T. Som, R. Fenger, M. Mohrmann,
A. Hoell, K. Rademann, J. Chem. Educ. 94 (2017) 510.
3. R. Fenger, E. Fertitta, H. Kirmse, A. F. Thünemann, K. Rademann, Phys. Chem. Chem. Phys.
14 (2012) 9343.
4. F. Erci, R. Cakir-Koc, I. Isildak, Artif. Cells Nanomed. Biotechnol. 46 (2018) 150.
5. B. A. Bello, S. A. Khan, J. A. Khan, F. Q. Syed, Y. Anwar, S. B. Khan, J. Photochem.
Photobiol. B Biol. 175 (2017) 99.
6. M. Ismail, S. Gul, M. I. Khan, A. Khan Murad, M. Asiri Abdullah, B. Khan Sher, Green
Proces. Synth. 268 (2018) 87.
7. S. Gul, Z. A. Rehan, S. A. Khan, K. Akhtar, M. A. Khan, M. Khan, M. I. Rashid, A. M. Asiri,
S. B. Khan, J. Mol. Liq. 230 (2017) 616.
8. S. A. Khan, S. B. Khan, A. M. Asiri, RSC Adv. 6 (2016) 83196.
9. S. A. Khan, S. B. Khan, A. M. Asiri, Sci. Rep. 6 (2016) 35107.
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM

14
|
S. A. Khan et al.
10. B. A. Bello, S. A. Khan, J. A. Khan, F. Q. Syed, M. B. Mirza, L. Shah, S. B. Khan, Biochem.
Biophys. Res. Commun. 490 (2017) 889.
11. S. Sohni, S. A. Khan, K. Akhtar, S. B. Khan, A. M. Asiri, R. Hashim, A. M. Omar, Colloids
Surf. A Physicochem. Eng. Asp. 549 (2018) 184.
12. S. A. Khan, B. A. Bello, J. A. Khan, Y. Anwar, M. B. Mirza, F. Qadri, A. Farooq, I. K. Adam,
A. M. Asiri, S. B. Khan, J. Photochem. Photobiol. B Biol. 182 (2018) 62.
13. M. Ismail, M. I. Khan, K. Akhtar, M. A. Khan, A. M. Asiri, S. B. Khan, Physica E: Low-dimens
Syst. Nanostruct. 103 (2018) 367.
14. C.-J. Jia, F. Schüth, Phys. Chem. Chem. Phys. 13 (2011) 2457.
15. S. Haider, T. Kamal, S. B. Khan, M. Omer, A. Haider, F. U. Khan, A. M. Asiri, Appl. Surf. Sci.
387 (2016) 1154.
16. S. A. Khan, S. B. Khan, A. Farooq, A. M. Asiri, Int. J. Biol. Macromol. 130 (2019) 288.
17. S. A. Khan, S. B. Khan, T. Kamal, M. Yasir, A. M. Asiri, Int. J. Biol. Macromol. 91 (2016) 744.
18. S. Ali Khan, S. Bahadar Khan, T. Kamal, A. M Asiri, K. Akhtar, Recent Pat. Nanotechnol. 10
(2016) 181.
19. S. B. Khan, S. A. Khan, H. M. Marwani, E. M. Bakhsh, Y. Anwar, T. Kamal, A. M. Asiri, K.
Akhtar, Rsc Adv. 6 (2016) 110077.
20. S. Gul, M. Ismail, M. I. Khan, S. B. Khan, A. M. Asiri, I. U. Rahman, M. A. Khan, M. A.
Kamboh, Asian Pacific J. Trop. Dis. 6 (2016) 311.
21. M. Ismail, M. I. Khan, S. B. Khan, K. Akhtar, M. A. Khan, A. M. Asiri, J. Mol. Liq. 268 (2018)
87.
22. J. Gao, J. Yu, Q. Lu, X. He, W. Yang, Y. Li, L. Pu, Z. Yang, Dyes Pigments 76 (2008) 47.
23. M. Ismail, M. I. Khan, S. B. Khan, M. A. Khan, K. Akhtar, A. M. Asiri, J. Mol. Liq. 260 (2018)
78.
24. A. N. Ejhieh, M. Khorsandi, J. Hazard. Mater. 176 (2010) 629.
25. M. Panizza, M. A. Oturan, Electrochim. Acta 56 (2011) 7084.
26. M. Jain, G. Misra, R. K. Patel, P. Priya, S. Jhanwar, A. W. Khan, N. Shah, V. K. Singh, R. Garg,
G. Jeena, Plant J. 74 (2013) 715.
27. Y. Gaur, A. Sen, New Phytol. 83 (1979) 745.
28. S. Gu, S. Wunder, Y. Lu, M. Ballauff, R. Fenger, K. Rademann, B. Jaquet, A. Zaccone, J. Phys.
Chem. C 118 (2014) 18618.
29. F. Al-Marhaby, R. Seoudi, World J. Nano Sci. Eng. 6 (2016) 29.
Supplementary Material: The online version of this article offers supplementary material
(https://doi.org/10.1515/zpch-2018-1297).
Brought to you by | Carleton University Library
Authenticated
Download Date | 9/8/19 1:05 PM