Date: 2019/12/17

Assignment Title
Mini Thesis on Interested Research Direction

Submitted by

Abro Mujahid Mehdi

20177215005
PhD student, Soochow university
Department of Textile and Clothing engineering

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

Robust Adsorption of Textile Effluent using Silk Nanofibres

Abstract
Here, the adsorption potential for anionic dyes (i.e., acid blue 117) from the aqueous medium of
electrospun silk nanofibres was assessed. SEM results indicated smooth surface morphology before and
after adsorption. XRD results further confirmed the proper crosslinking of silk nanofibres in order to
make them water insoluble. Surprisingly, electrospun silk nanofibres showed a great potential in the
removal of acid blue 117 from aqueous medium, i.e., 98% adsorption within a 1-min interaction time.
FTIR results also confirmed that multiple interactions between the dye and substrate caused the fast
adsorption of acid dyes. Therefore, the above-described results reveal that electrospun silk nanofibres are
a suitable choice for the removal of acid blue in real-time applications.

Keywords: Silk; Nanofibers; Electrospinning; Adsorption; Textile Effluent

1. Introduction
Coloration steps are basic/fundamental in many industries including textile, paper and paint, resulting in a
huge amount of toxic water-soluble dyes in wastewaters/effluent. The textile industry has been considered
as one of the main polluters of water, due to the huge consumption of water in coloration processes. It is
reported that about 20% of the dye is lost in the coloration process and drained with wastewater/effluent.
Generally, effluents generated from the aforementioned industries are complex in composition, highly
coloured and contaminated, as well as contain a high level of organic products, which are hard to
biodegrade. Hence, cleaning these waste dyes from effluent is considered as an important topic all over the
world [1-5].
Acid blue 117 (AB 117) is an anionic dye, composed of azo groups (-N=N-) in the aromatic ring of the
chemical structure. The presence of amine groups in acid dyes makes it highly toxic and hard to biodegrade
[6]. Moreover, continuous contact with this dye can generate dysfunctions in the liver, kidney, brain and
reproductive systems [7].
There are various techniques used to remove these toxic effluents, including ion exchange, adsorption,
membrane filtration, coagulation and flocculation, photochemical degradation, and ozonation [8].
Adsorption is considered as one of the most promising and environmentally friendly techniques for the
removal of toxic dyes from effluent. Further, it is a fast, easy, economical, byproduct-free and simple
technique [9]. Concerning secondary challenging aspects, i.e., powder removal after finishing the process

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

for regeneration or disposal, electrospun nanofibre membranes are considered as an effective alternate
option [10-16].
Due to its mechanical high strength, good biocompatibility with cell proliferation and adhesion, silk is
an interesting area of research for scientists and researchers [17-21]. Silk is a natural protein fibre produced
from silkworms. Aromatic repeat units and the presence of amino acid groups endow silk fibres with
excellent physical and chemical properties [22,23]. Recently, silk nanofibres have also been produced via
electrospinning [17].
Therefore, the promising properties of silk, especially the presence of amino groups and carboxyl in their
aromatic ring and the large surface area of electrospun silk nanofibres, inspired us to assess their adsorption
potential for acid dyes (AB 117). We believe that these azo functional groups and carboxyl sites present in
the aromatic ring of silk nanofibres will enhance the adsorption process and increase the removal efficiency
of acid dyes because amino groups have an affinity with sulphonate ions present in acid dyes. Further, to
the best of our knowledge, silk nanofibres have not been used to date for the adsorption of anionic dyes
from wastewater. Therefore, our main objective is to investigate dye removal potential of silk nanofibers
and design a scientific approach for dye removal.

2. Literature Review
2.1. NANOTECHNOLOGY
Nanotechnology or nanotech refers the modification of maneuver substance on an atomic, molecular,
and super molecular structure with its one dimension size of 1-100 nanometers, this ratio of nanometer
to a meter can be equivalent as, the ratio of tennis ball to earth [23].
2.1.1. Nanomaterials
Nanomaterials has gained a great interest in wide range of application such as textile, biotechnology,
medical, environment, electronics, and many others. This is due to their unique functional properties
in various forms [24]. Nanomaterials are classified into two main types (i) naturally occurring and (ii)
fabricated. The natural nanomaterials exist in the biological system such as viruses (capsid), which is
found in our bone matrix. Whereas the artificial or fabricated nanomaterials are exist into four different
forms [25]. These including Carbon based, Metal based, Dendrimers and Composite based
nanomaterials.
Carbon based nanomaterial These nanomaterials are carbon originated that exist in altered forms
such as hallow spheres, tubes or ellipsoids and nanotubes of carbon which is present in cylindrical
shape.

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

Metallic based nanomaterials These nanomaterials composed of metal oxides, nanosilver, nanogold
etc.
Dendrimers: These nanomaterials are exist in the form of branched units and adopts sphere-shaped
three dimensional morphology, there are components of dendrim a center core, internal structure, and
external functional group. These nanomaterials are mostly used for energy harvesting, drug delivery,
catalysis and etc.
Composites nanomaterials Composed of different types of nanoparticles that can be any combination
of polymer based nanomaterials, metallic, carbon or the composite.
2.1.2. Nanofibers
Nanofiber is a form of nanomaterials having diameter of micrometers to submicron or nanometers, the
mazing characteristics of nanofibers such as large surface area to volume ratio, flexibility and good
mechanical strength making these materials highly effective in various applications especially in water
and wastewater treatment, when compared to other forms of nanomaterials [26].
2.1.3. Nanofibers Production.
There are number of methods for producing nanofiber like; template synthesis, drawing technique,
self-assembly, phase separation, electrospinning and others. Amongst these methods, electrospinning
is one of the highly acknowledged process to fabricate functional nano to micro scale fibers. This is
comparatively easy and low cost method to produce large numbers of different nanofibers at higher
rate of production [27].
2.2. ELECTROSPINNING SET-UP
There are three main components of electrospinning process (i) high voltage power supply (ii)
grounded collector and (iii) the syringe pump as shown in the Fig-2.1 Electrospinning is a fiber
production technique in which different polymers are used to obtain nanofibers with diverse
formations; such as hollow, ribbon-like, aligned, core-shell and porous nanofibers. This process is
particularly suitable to produce the fibers with large and complex molecules [28].

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

Fig-2.1 Schematic diagram of electrospinning of polymer solution

2.2.1. Mechanism of Electrospinning
The simple mechanism of nanofibers production depends upon electrical charges or filed. First a
polymer solution of any material is taken into a plastic syringe and placed on a syringe pump, the
syringe pump will continuously push the syringe so that solution pass through the hole of spinnerate.
A high voltage from 10-40kv depending upon the nature of polymer is applied to the tip of polymer
solution, that will charge the droplet of the polymer solution and electrostatic repulsion force will be
counteracts the surface tension resulting stretching of droplet. When the viscosity of polymer solution
is adequate then steam will break and charge jet will be formed, the jet will be stretched out due to
whipping process caused by the electrostatic repulsive force which makes the small bends in the fiber
and finally collected on the collector.
2.2.2. Influential Parameters of Electrospinning.
There are three leading parameters of electrospinning; (i) parameters of polymer, (ii) processing
conditions, under which electrospinning is to be conceded and (iii) outer environmental conditions
(Ramakrishna, 2005) [29]. In order to produce uniform nanofibers all these parameters are essential to
be optimized in the electrospinning process. The solution parameters are the most importance
parameter to be considered for electrospinning. These including, molecular weight and its distribution,

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

surface tension, viscosity, conductivity, and concentration of the solution (Ramakrishna, 2005). The
viscosity of the polymer solution is affected by the molecular weight and concentration; therefore it’s
essential to produce uniform solution with certain viscosity in order to produce bead free nanofibers
from the polymer solution.
On the other hand, processing conditions such as applied voltage, feeding rate, distance from tip to
collector, needle diameter and collector type (Ramakrishna, 2005) must be established to fabricate
nanofibers. The voltage in the electrospinning process must be in the limit, increase in the voltage will
affect the stretching of solution as a result thinner fibers will be produced. Likewise, tip to collector
distance that leads to change in the electric filed, the feeding rate is preferred to be lower rather than
high for the evaporation of solvent. The diameter of needle is another factor which impacts the
consistency and morphology of electrospun nanofibers. Therefore it is essential to use appropriate
needle diameter as per solution viscosity, smaller the diameter of needle smaller will be polymer
droplet at the tip of spinneret. The collector must be enclosed with a conducting material like aluminum
foil, so that deposition of nanofibers on the collector increased. Moreover, type of collector used also
effects the assembly the nanofibers structure for example to achieve the aligned nanofibers rotating
collector system is needed [Ramakrishna 2005]. Environmental conditions could also impact on the
morphology as well as continuity of electrospinning these condition including humidity, temperature
and pressure [30]. If the temperature of the solution set to increased surface tension and viscosity will
be decreased. Therefore increase in temperature cause decreases in the average fiber diameter [Wang
et al., 2007][30-31]. On the other hand, the increase in humidity slow down the rate of solvent
evaporation, which cause increases in the average diameter of fiber.
2.2.3. Applications of Electrospun Nanofibers

Fig-2.2 Applications of Electrospun Nanofibers

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

2.3. STATEMENT OF PURPOSE

Pakistan is an agricultural country. Most of its population relies on the supply of pure and clean water.
But unfortunately due to increasing pollution level and many industrial and agricultural activities,
water system gets polluted with number of chemicals and toxic dyestuff discharge from coloring
industries that cause many health issues and biotic process disturbance. Due to improper guideline
values and insufficient treatment techniques particularly for dye polluted wastewater, we are trying to
introduce adsorption as a simple and easy technique that could excavate toxic dyes (present in low
level to high level concentrations). Nanofibers have high surface area ratio to volume. And it’s believed
to behave as an attractive media in aqueous media. We aim to prepare cheap, easily available polymeric
nanofibers to treat dye loaded water systems for maximum exclusion of synthetic dyestuff to get clean
water. The experimental factors influencing dye removal such as pH, contact time, nanofiber feed, dye
initial concentrations will be studied to develop environmental friendly removal method. The prepared
nanofibers will be analyzed via batch and continuous/filtration adsorption method to demonstrate the
feasibility of our proposed developed method.
Current study focus on evaluation and comparison efficiency of the silk as a electrospun nanofiber
membrane with previously reported literature on nylon, for the elimination of the anionic dyes from
aqueous phase.
2.4. OBJECTIVES
i. Fabrication of silk nanofiber membrane via Electrospinning.

ii. Characterization of silk membrane before and after dye removal.

iii. Determination of removal efficiency of Anionic dyes from waste water.

iv. Calculation of adsorption kinetics and isotherms.

2.5 SCOPE OF STUDY

➢ The proposed work may help developing easy, cheap and reliable method of treating dye polluted
water through electrospun nanofibers from indigenous and abundant in nature silk polymer.

➢ The work may be adapted to industrial scale from laboratory scale experiments by integrating
nanofiber membranes to filtration unit in order to achieve pure water through cheap materials.

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

➢ The work may also generate patents through extensive knowledge of adsorbent material being
utilized in dye water treatment.

➢ The work can not only be used to capture dye molecule from water but also number of other toxic
pollutants such as metals, pesticides, plasticizers, pharmaceuticals can be removed through the proper
knowledge of properties of both adsorbent and adsorbate molecule. Nanofibers morphology and
physical parameters such as surface area, porosity are crucial factors in making promising material for
adsorption studies; therefore, this work covers complete scope of study in engineering and other
aspects of science and technology.
2.6. WASTEWATER TREATMENT TECHNOLOGIES
There are number of technologies, such as biodegradation, chemical oxidation, advanced oxidation,
electrolysis, ion exchange, and photo catalysis and adsorption process have been applied for removal
of dye loaded effluents. But most of these methods have numerous weaknesses such as incomplete
pollutant removal, high-energy consumption, and generation of toxic sludge. (Ferroudj et al., 2013).
Below the litterateur given showing the removal of dyestuff using different nanofibers membrane.
Mansour Anbia et.al (2011). In this work, SBA-3 ordered mesoporous silica was used as
nanoadsorbent for the elimination of acidic dyestuff (AO-67, AB-113, AR-114, AY-127 AG-28) from
aqueous solution. The SBA-3/PEHA has proved to be greatly effective for the exclusion of the acid
dyes within 60min of equilibrium time. The pH of dye solution has a significant impact on the
adsorbent efficiency towards acid dyes, reduction in pH of the solution leads to increase in the
adsorption capacity of SBA-3/PEHA.
Emna Errais et.al (2011). Present research focus on the anionic dye adsorption (RR-2) through
untreated natural clay as a low cost adsorbent material. The experimental data shows that adsorption
efficiency increased with decrease in pH value, the maximum efficiency was observed after 80-100
min. furthermore adsorption rate was also effected due to rise in temperature which is exothermic
process.
S. Swaminathan et.al (2015). In this study composite nanofibers of graphene oxide and waste yarn of
polyacrylonitrile was prepared for the elimination of methylene blue dye. It was found that at basic pH
is suitable to achieve maximum dye exclusion by the1.5 weight% of graphene oxide and waste yarn of
pan. It was found to that efficiency was maximum 90.5 % at basic pH8 which was attend after the 7
hours of contact time.
S.Nethaji et.al (2013). In this research carbonaceous particles were used for anionic and cationic dyes
removal. The carbonaceous particles prepared from Juglans regia shells through acid treatment method.

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

The adsorption of two dyes namely malachite green as a basic dye and amido black 10B as an acid dye
were carried out though batch method under influential parameters such as ;pH, dosage, initial
concentration. The experiential results reviled that adsorption of MG and AB was maximum at pH 6-
8, and 2-2.3 respectively. Moreover, 3g/l of JSAC is capable to achieve 100% adsorption of MG with
initial concentration of 25mg/l, while at same dosage 90% of efficiency was observed for AB.
Niyaz Mohammad Mahmoodi et.al (2015). PVA-chitosan blended nanofibers was used in this
research paper for the elimination of (DR80), (DR81) and (RR180) as anionic dyes. From the
experimental consequences, it was observed that adsorption rate improved as the pH of the dye solution
reduced. The maximum adsorption by the blend nanofiber was found to be (70-80 %) at (t: 90 min,
C0=20 mg/l, T=25 oC, dosage 0.016g) for the above dyes.
Aihua Pei, et.al. (2013) in this research work cellulosic nanofibrils was synthesized through
disintegration from wood pulp and pre-treated with glycidyltrimethyl ammonium chloride. Q-NFC
nanofibrils was used an adsorbent material for the confiscation of Congo red and acid green 25 dye.
The (30 mg) of Q-NFC nanofibers was placed in 0.5 mg mL_1 Congo red solution which takes 24
hours of contact time to removal 75% dye removal when time was further increased to 72 hours the
removal efficiency reached to 95%.
A.A. El-Bindary1 (2016) .The adsorption behavior of reactive blue 19 dye (RB19) from aqueous
solution, onto rice straw and fly-ash (RSFA) was examined to determine the capability of waste
adsorbent to eliminate dyes. Efficiency of RSFA towards the RB19 was found to be 85% within 60min
at 0.09 g of adsorbent dosage with initial concentration of 30-100mg/L at pH 1.
Mozhdeh Ghani,et.al (2014). In this study composite nanofiber of Polyamide-6/Chitosan was
fabricated though electrospinning technique for Solophenyl Red 3BL, as an acidic dye and Polar
Yellow GN, as direct dye removal. It was observed that, the chitosan ratio on dye elimination efficiency
was favorable, while the effect of increasing the pH solution value and initial concentration were
negative, the maximum efficiency was achieved at the lowest pH and the highest chitosan ratio.
T. Santhi,et.al (2010). In this work activated carbon which was synthesized from annona squmosa
seed was utilized for the confiscation of methyl red from simulated dye solution. This is inexpensive
and ecofriendly material which has great potential for dye exclusion. From the experimental data it
was observed that removal efficiency is proportional to dosage of adsorbent at optimum pH 4, it takes
50min to achieve the removal efficiency of 82.81% at the initial concentration of 25ppm and room
temperature.
Khalid Mokhlif Mousa (2016). In this study, adsorption process is carried out for both using natural
wheat straw (NWS) as low cost adsorbent, modified wheat straw (MWS) and Activated Carbon (AC)
Student Name: Abro Mujahid Mehdi
Student ID: 20177215005
 Date: 2019/12/17

for comparing the results. The effect of pH was determined by adjusting pH values (2.5 – 10.5). To
study the effect of initial dye concentration, six different concentrations of reactive blue dye (5, 20, 30,
50, 70 and 90) mg/L was prepared Results showed that the removal percent using NWS, MWS and
AC are; 68%, 92.17% and 90.5% respectively. Equilibrium isotherm experiment were carried at
different dosages (0.1 – 1 g).
Ihsan Habib Dakhil (2016) . The aim of this work is a comparison study among three low cost
adsorbents [Sawdust "SD", Spend tea leaves "STL", Rice husk "RH"] for removal of Methylene blue
(MB) dye through batch experiments. The results shows that maximum adsorption was achieved after
120 min of contact at minimum dosage of 0.6gm at neutral pH. The experimental data were analyzed
and compared with Langmuir and Freundlich isotherm models. Langmuir model is found very well
represent the equilibrium data with correlation factor is close to unity than the Freundlich model.
Foza Foroozmehr(2016). In this work blended nanofiber of PAN with beta CD used to treat reactive
dyes. Results show that dye removal efficiency was increased from 15.5% for PAN to 24% for
PAN/βCD nanofiber mats. The low efficiency of PAN/βCD membranes was due to the decrease in the
βCD content during the filtration process because of the high solubility of βCD in aqueous solutions
the decrease in the water solubility of βCDP, the βCDP content in nanofibers didn’t change during
filtration.
Arash Almasian (2015) The diethylenetriamine (DETA)/polyacrylonitrile (PAN) composite
nanofibers were prepared by using electrospinning technique for the removal of anionic direct dye The
amount of the dye adsorbed onto the PAN/DETA nanofiber mats was influencedby the initial pH,
DETA amount, contact time, and the initial concentration of the dye solutions. The results shows that
maximum adsorption efficiency was 100% at acidic pH, with initial dye concentration of 40mg/l with
dosage of 0.004g.

3. Experimental

3.1 Preparation of Silk Precursor

A formerly available method was followed to prepare silk precursor [17]. Briefly, B. mori silkworm
cocoons were boiled in an aqueous solution of 0.5 % (w/v) NaHCO3 for 1h and washed with deionized (DI)
water several times to remove sericin maintaining the temperature of 60°C. The degummed SF fibers were
dissolved in 9.3 mol·L-1 LiBr solution at 60°℃ for 1 h. The regenerated SF aqueous solution was obtained

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

after dialysis in DI water using dialysis tube (MWCO 6000-8000 Da, Spectra/Por, USA.) for 3 days to
remove the LiBr salts. Finally, the obtained solution was lyophilized to get the silk fibrins.

3.2 Preparation of Silk Nanofibers

Silk precursor was put in hexa fluro 2 propanol with concentration of 4% w/w% and left for stirring for 12
hours at room temperatureto achieve electrospinning solution. The silk nanofibers were obtained via
electrospinning as shown in Figure 1a below. Briefly, the solution was placed in a 5 ml syringe with a 22
gauge needle. A 12 kV voltage was applied on needle at 0.8 ml/hr feed rate. Electrospun nanofibers were
collected on a rotating drum covered with aluminum foil, which was placed at a distance of 12 cm from the
needle tip. The nanofibrous membrane was peeled off and dried at fume hood (overnight). Finally,
membrane was immersed in 75% ethanol for one hour in order to achieve crosslinked silk nanofibers.

3.3 Material Characterization

SEM samples were coated with gold and examined at an accelerating voltage of 15 kV on FE-SEM (S-
4800; Hitachi Ltd. Japan) in order to analyze surface morphology of silk nanofibers before and after
adsorption. While, Chemical structure of silk nanofibers before and after adsorption was assessed using
FTIR spectroscopy (Thermo Nicolet 5700, Thermo Fisher Scientific Inc. USA). The crystallinity of silk
nanofibers before and after adsorption was investigated through XRD (model D/max-IIB, Rigaku). The
adsorption studies were evaluated on UV-Vis spectrophotometer.

3.4 Dye Adsorption Experiment

Adsorption assessment of anionic dyes with silk nanofibers was done with: batch-wise method. For batch
experiments, mass of 20 mg silk nanofibers was shacked with 5mL of AB117 dye solution (50 mg/L).
Adsorption parameters were optimized to find the optimum conditions as adsorption time (0-3mins), pH
(3-11), mass of nanofibers (10-40 mg), initial dye concentration (25-400 mg/L). The dye removal efficiency
(AE%) was measured using following equation (1):

𝐶𝑎
𝐴𝐸% = (1 − ) × 100 1)
𝐶𝑏

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

Where Cb and Ca (mg/L) are the before and after concentrations of dye observed after dye-silk interaction.
The maximum adsorption capacity qe (mg/g) of silk nanofibers was also measured using following equation
(2):

𝑉
𝑞𝑒 = (𝐶𝑏 − 𝐶𝑎 ) × 2)
𝑚
Where V is the volume (L) of dye bath and m is the mass of silk nanofibers (g). Furthermore, confirming
the linear fitting of kinetic and isotherm models apart from regression co-efficient (R2), sum of squared
errors was also measured using the equation (3):

2
𝑆𝑆𝐸 = ∑𝑁
𝑖=1(𝑞𝑐𝑎𝑙 − 𝑞𝑒𝑥𝑝 ) 3)

Where qcal and qexp (mg/g) are the measured and experimentally explained adsorption capacities of silk
nanofibers. The smaller the SSE values, the better will be the corresponding fitting.

4. Result and Discussion

4.1 Surface Morphology

Surface morphology of pure silk nanofibers and crosslinked silk is shown in Fig.1 a-b respectively. It was
observed that pure silk nanofibers having an average diameter of 200 nm, were uniform and bead free. After
crosslinking the silk nanofibers with 75% ethanol, diameter of silk nanofibers was increased from 200 to
250nm [24] but morphology of nanofiber structure was remained unaffected and stable.

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

Fig.1 Surface morphology and diameter distribution of electrospun Silk nanofibers; A) SEM image of
pure silk nanofibers, B) SEM image of crosslinked silk nanofibers

4.2 Chemical Analysis

In order to understand primary and secondary structure of electrospun silk nanofibers, the pure and cross-
linked structures of silk nanofibers (treated with 75% ethanol) were examined using XRD. Here we refer
primary structure as pure silk nanofibers (Silk I) and secondary structure (Silk II) as cross-linked silk
nanofibers. In Fig.2, broad peak at 22.4 o of pure silk nanofibers shifted to 19.7 o after treating in ethanol.
This peak shifting validates the transition of silk I towards silk II nanofibers and attained good stability in
aqueous solution [24]. Fourier transform infrared spectroscopy (FT-IR) of pure silk nanofibers, cross-
linked silk nanofibers (treated with 75% ethanol) and dye-adsorbed silk nanofibers was taken, in order to
evaluate the chemical structure of pure silk nanofibers and if any changes in chemical structure, occurred
after interaction with ethanol (for cross-linking) and dye (acid blue 117) for adsorption. From Fig.3 a-d,
two strong peaks with their Centre around 1647 cm-1 (amide Ⅰ) and 1546 cm-1 (amide Ⅱ) along with
several regions of proteins between 2800 cm-1 – 3650 cm-1 of pure silk nanofibers were observed, are in
good agreement with previous reported works of silk nanofibers [25,26]. Whereas, these adsorption peaks
of amide Ⅰ (at 1647 cm-1) and amide Ⅱ (at 1546 cm-1) were shifted to 1627 cm-1 and 1523 cm-1 after
treating silk nanofibers with ethanol (75 %, v/v) confirms the transmittance of adsorption peaks and hence
cross-linking of silk nanofibers [27, 28]. Likely, effect of dye interaction on chemical structure of silk
nanofibers can be asserted from Fig. 3b; which reveals a slight change in intensities of peaks besides
improving of N-H stretching, proposes addition of N-H (amino group) from dye (acid blue 117) in the silk
nanofibers. While, decrement in band intensities of amide1 and amide11 groups occurred may be due to
contribution of N-H and C=O sites for acid blue 117 adsorption [29]. Surprisingly, two new peaks of SO3
(b/w 1022-1030 cm-1) and SO2 (at 930 cm-1) were also observed. These new peaks further ratify that
adsorption of dye took place by reason of compound interactions b/w acid blue 117 and silk nanofibers
[30].

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

Pure Silk
Cross Linked Silk

19.7

intensity (a.u)
22.4

10 20 30 40
2 ( )

Fig.2 XRD spectra of pure and crosslinked silk nanofibers

Fig.3 FTIR spectra A) Full range FTIR spectra of pure, crosslinked and adsorbed silk nanofibers, (B, C &
D) Magnified range of pure silk, crosslinked silk and adsorbed silk respectively for chemical analysis

4.3 Batch dye Adsorption

4.3.1 Effect of Time

The Fig.4a show the UV-vis spectrum peak of acid blue 117 dye at 50 ppm dye concentration and indicates
the initial value of dye concentration for measurement. The Fig.4b show the effect of interaction time on
adsorption of acid blue 117 on silk nanofibers evaluated at different time intervals (from 15 sec-180 sec)
with 50 mg/L of dye concentration. Surprisingly, silk nanofibers shown a remarkable and rapid adsorption
of dye (acid blue 117) within 45 sec (80%) which reached to max: absorption within 60 sec (98 %) and
attained equilibrium within that same passage of time. To the best of our knowledge, this is the fastest
adsorption of dye (acid blue 117) by any nanofibrous adsorbent; reported so for. Based on chemical
characterization results it can be assumed that this rapid and efficient adsorption was occurred due to strong
interaction of N-H and C=O groups -present in the silk nanofibers -with of acid blue 117 dye [31].

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

Fig.4 A) UV-visible spectrum of Acid blue dye, B) Adsorption efficiency of Silk nanofibers for Acid blue
with respect to time (Seconds)

4.3.2 Effect of PH

Effect of pH on adsorption ability, is an important factor to understand as it has direct influence on the
active sites present in the surface of proline based polymers [32] and hence the adsorption ability. The
Fig.5b illustrates that the acidic range is much effective for dye removal from aqueous solution as maximum
removal efficiency attained at pH value of 5. This increase in dye adsorption potential at acidic pH is
assumed as an increase in positive charges on the surface of silk nanofibers to attract more negative charged
acidic dyes [33].

Fig.5 A) Effect of Mass on adsorption of acid blue dye onto silk nanofibers, B) Effect of pH on
adsorption of Acid blue onto silk nanofibers,

4.3.3 Effect of Mass of Nanofibers

The effect of mass of silk nanofibers on adsorption is given in Fig.5a. An increase in adsorption of acid
dyes was observed when mass of silk nanofibers was selected from 10mg-40mg and shacked gently for 1
min at room temperature. This increase in adsorption performance is due to the large area and so the
increased active sites to attract acid blue117 [34].

4.3.4 Effect of dye Concentration

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

The influence of dye concentration on its removal performance with silk nanofibers is shown in Fig.6a. The
results reveal that by increasing the dye concentration ranges from 25-400 mg/L, the adsorption
performance declined from 98 % to 65%. This drift can be clarified with the fact that the silk nanofibers
own a limited number of active sites to attract dye molecules. This assumption is further proved from Fig.
6, which asserts that the adsorption capacity increases linearly with increasing dye concentration and max
adsorption is observed 66.2 mg/g.

4.4 Adsorption Isotherms

The adsorption isotherm studies are used to recognize the behavior of molecules distribution between the
solid phase and the liquid phase using Langmuir and Freundlich. The equilibrium studies were showed for
20 mg silk nanofibers in 5 ml solutions, where the concentration of acid blue 117 dye was varied from 25
to 400 ppm. After 60 seconds, the residual concentrations of acid blue 117 dye ‘Ce’ were measured. Fig.6
shows that the adsorption capacity of silk nanofibers increases gradually with increasing concentration of
acid blue dye.
To study the behavior of adsorption of acid blue dye on silk nanofibers, the Langmuir isotherm equation
used for calculation is expressed as:
𝐶𝑒 𝐶𝑒 1
= + 4)
𝑞𝑒 𝑞𝑚 𝐾𝐿 𝑞𝑚

Where ‘qe’ (mg/g) is the amount of acid blue dye adsorbed by silk nanofibers, ‘Ce’ (mg/L) is the residual
concentration of acid blue dye, ‘KL’ (L/mg) is the energy of reaction and ‘qm’ (mg/g) is the maximum
adsorption capacity at equilibrium. The values of ‘KL’ and ‘qm’ were determined to form the slop and
intercept of a linear plot of ‘Ce/qe’ against ‘Ce’. When adsorption equilibrium achieved, the findings of the
present study fitted to the Langmuir isotherm model, which supports occurring of monolayer adsorption
with a limited number of adsorption sites. The silk nanofibers displayed the maximum adsorption capacity
of 66.2 mg/g using Langmuir isotherm, whereas ‘KL’ and ‘R2’ are observed to be 0.05 and 0.91, respectively
as shown in Table 1.
The Freundlich equation is expressed as:

1
𝐿𝑜𝑔 𝑞𝑒 = ( ) 𝑙𝑜𝑔𝑐𝑒 + 𝑙𝑜𝑔𝐾𝑓 5)
𝑛

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

Where ‘Kf’ (mg/g) is the adsorbent capacity and ‘1/n’ is sorption intensity of the adsorbent. The
determined values of Freundlich isotherm as shown in Table 1 which indicate that the experimental data
followed Langmuir isotherm more than Freundlich isotherm.
The separation factor ‘R2’ of Langmuir isotherm is an important feature that is used to test the feasibility
of the process, and it was calculated using Eq.(6):

1
𝑅𝐿 = 6)
1+1(𝐾𝐿 𝐶𝑖 )

Where ‘Ci’ is the concentration before adsorption and ‘KL’ is Langmuir constant, the energy of adsorption.
The value of ‘RL’ indicates the nature of adsorption whether it is favorable (>0 or <1), unfavorable (>1)
linear (=1), or irreversible (=0). Thus, in the present study, the calculated value of ‘RL’ is found to be 0.285
(>0 or <1), suggesting favorable adsorption of acid blue dye on the silk nanofibers.

4.5 Adsorption Kinetics

The kinetic study of acid blue dye adsorption on SNFs nanofibers was carried out to determine the time
equilibrium, the time required in this process and adsorption rate of acid blue dye on silk nanofibers. The
experiment was carried out at 50 ppm concentration of acid blue dye at optimum conditions. It was observed
that the adsorption of acid blue dye is 98% within 60 seconds. Consequently, after 180 seconds, the removal
rate gains equilibrium.
Pseudo 1st order equation (7) was used to analyze the adsorption rate constants.

ln(𝑞𝑒 − 𝑞𝑡 ) = 𝑙𝑛𝑞𝑒 − 𝑘𝑡 7)

Where ‘qe’ is the amount of adsorbed dye at equilibrium and ‘qt’ is the amount of acid blue molecules
adsorbed at time ‘t’ (min). The calculated coefficient of determination ‘R2’ was not fit.
On the other hand, Pseudo-second order equation was also used in order to determine the nature of the
interaction:
𝑡 1 1
= ( )𝑡 + 2 8)
𝑞𝑡 𝑞 𝑒 𝐾 2 𝑞𝑒

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

Where ‘qe’ is the adsorption capacity, ‘K’ is rate constant and coefficient of determination ‘R2’ are
obtained from the linear graphs between (t/qt and t). Whereas, the calculated adsorption capacity and
theoretical adsorption capacity were in good agreement with each other while giving correlation regression
value ‘R2’ of 0.981. Furthermore, the kinetic adsorption study reveals that the interaction between acid
blue dye and silk nanofibers was well chemical interaction in nature.

Table 1. Adsorption isotherm of Silk nanofibers

Isotherm
Nanofibers
Langmuir Freundlich
qe R2 KL SSE 1/n R2 Kf SSE
Silk Nanofibers 66.20 0.91 0.05 0.392 0.345 0.873 9.502 2.066

70
100
Adsorption efficiency, %
Adsorption capacity, mg/g 60

Adsorption capacity, mg/g

Adsorption efficeincy, %

90 50

40
80
30

20
70
10

60 0
0 50 100 150 200 250 300 350 400
Concentration, ppm

Fig.6 Adsorption efficiency and capacity curves of silk nanofibers with respect to dye concentration

5. Conclusion

Summarizing, we successfully prepared silk nanofibers via electrospinning in order to assess their
adsorption potential for acid blue 117. As prepared electrospun silk nanofibers were cross-linked with
ethanol before adsorption studies which make silk nanofibers stable in aqueous phase applications. SEM
and XRD analysis confirmed cross-linking of silk nanofibers. All the adsorption parameters (Time, pH,
mass of nanofibers, dye concentration, etc.) were optimized. A 20 mg silk nanofibers shown 98 %

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

adsorption of acid blue (dye concentration 50 mg/L) within 1-minute interaction time at pH 5. To the best
of our knowledge, this is the fastest adsorption potential of any nanofiber for acid dyes so for. FTIR results
also validated that this fast adsorption took place due to multiple interactions between dye and substrate.
Therefore, proposed material is highly recommended due to its efficient removal potential in terms of
capacity, time, and removal performance.

6. Acknowledgment

The work was supported by National Engineering Laboratory for Modern Silk, College of Textile and
Clothing Engineering, Soochow University, Suzhou 215123, China.

Student Name: Abro Mujahid Mehdi

Student ID: 20177215005
 Date: 2019/12/17

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Student Name: Abro Mujahid Mehdi

Student ID: 20177215005