Research Article

Cite This: ACS Sustainable Chem. Eng. 2019, 7, 1159−1168 pubs.acs.org/journal/ascecg

Visualized Fibrous Adsorbent Prepared by the Microwave-Assisted

Method for Both Detection and Removal of Heavy Metal Ions
Sheng Deng, Guangshan Zhang,* and Peng Wang*
State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, No.73
Huanghe Road, Harbin 150090, China
*
S Supporting Information

ABSTRACT: In the present study we synthesized a dual-

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functionalized material by incorporating a chromophore, 4-(2-

pyridylazo)-resorcinol (PAR), onto polyacrylonitrile (PAN) fiber
by microwave (MW) irradiation; the produced material was
labeled PANMW-PAR. Compared with conventional methods,
MW irradiation exhibits superior advances in reaction time and
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grafting rate of surface modification, further resulting in

satisfactory colorimetric and adsorption properties. A systematic
study has been implemented to analyze the detection and
removal ability for heavy metal ions, including Hg2+, Cu2+, Pb2+,
and Ni2+. Results demonstrated that PANMW-PAR fibers possess
impressive colorimetric sensitivity (red-to-black color change)
and high adsorption capacity for these metal ions, especially for Hg2+. Thus, these fibers present excellent potential as optical
sensors and adsorbent for heavy metal contaminants. At low pH, the PANMW-PAR fibers showed selective detection ability for
Hg2+, and the detection limit can be obtained at 35 μg/L. Adsorption of heavy metal ions followed pseudo-second-order
kinetics and Langmuir isotherms. X-ray photoelectron spectroscopy provided insights into the interaction mechanism between
heavy metal ions and PANMW-PAR fibers. PANMW-PAR fibers can be feasibly regenerated with EDTA and still exhibited high
sensitivity and adsorption affinity for heavy metal ions after 10 cycles of reuse. The proposed fibers present a cost-effective
material that can be considered an alternative for effective detection and removal of toxic metal ions from water.
KEYWORDS: Optical detection, Removal, Heavy metal ions, Microwave irradiation, Polyacrylonitrile fiber

■ INTRODUCTION
With increasing generation of metals from technological
activities, the problem of heavy metal ion wastewater discharge
has become extremely important.1−4 In addition, sudden heavy
metal pollution has exposed larger detriments than regular
heavy metal pollution. In recent years, the occurrence of
sudden heavy metal pollution in China happened with enough
regularity, such as illegally discharging a large amount of
cadmium into the Longjiang River in Guangxi Province at
2012 which caused severe pollution and induced public panic
and sudden chromium pollution in the reservoir in Qujing City
of Yunnan Province in 2011.5,6 Due to the high uncertainty of
a sudden water pollution accident, the pollutants would spread
rapidly and cause extensive detriments.7 Thus, it is still a large
challenge to develop new materials for heavy metals detection
and removal from water.
Many approaches have been adept to remove heavy metal
ions from water; 8−13 however, most of them reveal
considerable disadvantages, including low removal efficiency,
large energy consumption, and generation of toxic secondary
pollutants. Among these known methods, adsorption is taken
for one of the most convenient, economical, prompt, highly
adaptable, and competent for scavenging of heavy metal ions
from wastewater.14−16 Recently, newly developed nanofibrous
membrane doped with metal organic frameworks (MOFs) has
been utilized to remove heavy metals ions.17−19 Simulta-
neously, apart from the development of removal methods,
various detection techniques were investigated for sensing
heavy metal ions; colorimetric detection has attracted
considerable attention due to its low cost and easy operation
for direct on-site and real-time visual analyses of heavy metal
ions in water,20,21 whereas materials with both removal and
detection abilities for heavy metal ions are less studied and
remain at an initial research stage. Yan et al. (2016) developed
pyromellitic dianhydride-grafted cellulose nanofibrous mem-
branes for simultaneous visual detection and removal of Pb2+;
this novel material exhibits a low detection limit and high
adsorption capacity for Pb 2+ .22 Sapana et al. (2016)
synthesized a new oxidized-cellulose-based material for
simultaneous detection and removal of Hg2+ from water.23
The detection limit and adsorption capacity of this Schiff-base-
based sensor for Hg2+ totals 10 mg/L and 121.2 mg/g,
respectively. Although these materials could detect and adsorb
metal ions from water, the synthesis routes were relatively
Received: September 20, 2018
Revised: November 3, 2018
Published: November 13, 2018

© 2018 American Chemical Society 1159 DOI: 10.1021/acssuschemeng.8b04760

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ACS Sustainable Chemistry & Engineering Research Article

tedious, complicated, and not suitable for sudden heavy metal Scheme 1. Synthesis Route of PAR-Immobilized PAN
pollution treatment. Thus, the development of such material Fibers via MW Irradiation
with both colorimetric and adsorption abilities as well as a
quick and simple preparation method induce significant
interest for treatment of heavy metal ion pollution in water.
Polyacrylonitrile (PAN) fibers are suitable matrix materials
for preparation of adsorbents due to their ultralarge surface
area, low flow resistance, high thermal and mechanical stability,
and recyclability.24−28 Few studies in the literature have
investigated PAN-based heavy metal ion sensors.29,30 However,
the preparation route of modified PAN fibers is tedious and
time consuming, resulting in low efficiency and less effective
properties. These results are mainly due to the relatively low
grafting rate of functional groups and nonuniform modification
initiated by conventional heating. The microwave (MW)-
assisted method, as an alternative method, has been utilized in
surface modification instead of conventional heating due to the
former’s ability to ensure rapid and uniform heating in the grafting rate. Reaction conditions, including fiber weight (A),
chemical reactions. Compared with the conducting mechanism reaction time (B), temperature (C), and ratio of EDA/water (V:V),
of conventional heating, the MW-assisted method produces were optimized in three varying levels, as described in Table 1.
efficient internal heating by direct coupling of MW energy with
molecules, whereas heat is generated directly or volumetrically Table 1. Investigated Variables and Their Levels
through two main mechanisms: dipolar polarization and ionic
levels of reaction
conduction.31−33 Consequently, rapid heating, uniform mod- each weight of time temperature ethylenediamine/water
ification, and improved yield and performance of the prepared variable fiber (g) (min) (°C) (V:V)
materials are usually obtained by the MW-assisted method. 1 1 30 105 1:1
In this study, we describe 4-(2-pyridylazo)-resorcinol 2 2 40 110 2:1
(PAR)-immobilized PAN fibers, which were prepared through 3 3 50 115 3:1
the MW-assisted method, as a visualized adsorbent to removal
of heavy metal ions from water. With three reactive groups
including the heterocyclic nitrogen group, azo group, and o- Typically, PANF, EDA, and deionized water (DI) water were put into
a 250 mL three-necked flask and stirred for 5 min until
hydroxyl group, PAR can coordinate firmly with different metal
homogeneously mixed. MW parameters in the reactor were set up,
ions and give a visually detected color change.34,35 PAR- and the reaction was refluxed under continuous mechanical stirring.
incorporated PAN fibers are readily accostable in regard to After reaction, the fibers were separated from the solution by filtration
heavy metal ion detection in water and exhibit a high and rinsed with hot water repeatedly. The obtained fibers (PANMW-
adsorption amount. The preparation parameters were opti- EDA) were placed on a glass plate and dried overnight in a vacuum
mized by the orthogonal method, and the effect of solvent on oven at 60 °C.
PAR immobilization under the MW-assisted method was Step 2. Attachment of PAR onto PANMW-EDA Fibers. Initially,
studied. The modified fibers were carefully characterized, and PAR (0.5 g) was dissolved and sonicated for 10 min in a mixture of
colorimetric performance, with adsorption abilities as a ethylene glycol (40 mL) and DI water (10 mL). Then the above
mixture, PANMW-EDA fibers (1.0 g), and HCHO (10 mL) were
function of pH, time, and different initial concentrations
successively added into the reaction flask, and nitrogen was bubbled
toward heavy metal ions, was thoroughly investigated.

■
EXPERIMENTAL SECTION
Chemical Reagent. Ethylenediamine (EDA), ethyl alcohol
(EtOH), ethylene glycol (EG), formaldehyde (HCHO), and 4-(2-
pyridylazo)-resorcinol (PAR) were obtained from Aladdin Chemical
Reagent Co., Ltd. (Shanghai, P.R. China). Polyacrylonitrile fibers
(PANF) with a specific gravity of 1.18 g/cm3 were purchased from
Beijing Ronel Industry Material Co., Ltd. (Beijing, P.R. China). Metal
ions’ solution for adsorption tests were prepared by dissolving
Hg(Cl)2, CdCl2·2.5H2O, Ni(Cl)2, CaCl2, Mg(NO3)2, Al(NO3)3,
Pb(NO3)2, Cr(NO3)3, and Cu(NO3)2·3H2O in Milli-Q water and
further acidized with 0.1% HNO3 (≥99.999% trace metals basis). All
of the other chemicals were of analytical grade (>99%).
Synthesis of PAR Immobilized Dual-Functional Material.
Functionalization reactions were performed in a commercial MW
reactor (COOLPEX-E, Preekem Scientific Instruments Co., Ltd.,
China) under a fixed temperature or fixed power. Figure S1 in the
Supporting Information (SI) illustrates the modules of the MW
reactor. Scheme 1 presents the schematic of the reaction route, and
the synthesis details are presented as follows.
Step 1. Amination of PAN Fiber. PAN fibers were first aminated by
EDA prior to PAR immobilization, and design of a L9 (34) orthogonal
matrix was adopted to investigate the effects of reaction conditions on
into the system to eliminate oxygen. The reaction was carried out in
the MW reactor with continuous mechanical stirring, and the output
power of the MW reactor was set at 200 W. Then the PAR-
immobilized fibers were filtered and rinsed at least 10 times repeatedly
with hot water. Subsequently, the fibers were extracted with water/
methanol (V:V = 1:1) solution in a Soxhelt apparatus for 12 h. Finally,
the fibers were vacuum dried overnight at 60 °C, and the obtained
product was named PANMW-PAR.
The grafting percentage (GP) was calculated by gravimetry through
the following equation
m − m0
GP = 1 × 100%
m0 (1)
where, for Step 1, m0 refers to the weight of PAN fibers and m1
denotes the weight of PANMW-EDA fibers. For Step 2, m0 represents
the weight of PANMW-EDA fibers and m1 stands for the weight of
PANMW-PAR fibers.
Characterization. The functional groups of PANF in different
modification stages were observed with aPerkinElmer spectrum 100
FT-IR spectrometer. UV−vis spectra were measured with a
PerkinElmer Lambda 950 UV/vis/NIR spectrometer. Differential X-
ray photoelectron spectroscopy (XPS) curves were recorded using a
Thermo Fisher ESCALAB 250Xi high-resolution XPS spectrometer
with an Al Kα X-ray source.

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Table 2. Result Analysis of Amination Reaction Orthogonal Experiment

factors
no. A B C D PAN (g) PANMW-EDA (g) GP%
1 1 1 1 1 1.0014 1.0760 7.449
2 1 2 2 2 1.0007 1.2725 27.16
3 1 3 3 3 1.0041 1.1914 18.65
4 2 1 2 3 2.0035 2.3953 19.56
5 2 2 3 1 2.0070 2.4967 24.40
6 2 3 1 2 2.0011 2.7825 39.05
7 3 1 3 2 2.9966 3.98 3 33.09
8 3 2 1 3 3.0025 3.8265 27.44
9 3 3 2 1 3.0077 3.7918 26.07
K1 53.26 60.10 73.94 57.92
K2 80.01 79.00 72.79 99.3
K3 86.61 83.77 76.14 65.65
k1 17.75 20.03 24.65 19.31
k2 26.67 26.33 24.26 33.1
k3 28.87 27.92 25.38 21.88
R 11.12 7.89 1.12 13.79
order D>A>B>C
optimal level A3 B3 C3 D2
optimal condition A3 B3 C3 D2

Colorimetric Detection of Heavy Metal Ions. First, 25 mL of
different heavy metal ions solutions was added into a 50 mL
colorimetric tube, and then the colorimetric detection tests were
performed by adding 10 mg of PANMW-PAR fibers into the solution.
Colorimetric assessment for PANMW-PAR fibers in various heavy
metal ions solution were visualized qualitatively with the naked eye
and quantified with UV−vis spectrometry.
Batch Adsorption Experiments of Heavy Metal Ions.
Typically, 10 mg of PANMW-PAR fibers was immersed into 50 mL
of heavy metal ions solutions with concentrations ranging from 20 to
200 mg/L. Then the bottle was placed on a SHA-C shaker by setting
the shaking speed at 100 rpm under mild temperature (25 °C).
Adsorption capacities of heavy metal ions were characterized by
testing metal ion concentration within aqueous solution before and
after adsorption using an inductively coupled plasma optical emission
spectrometer (ICP-OES). The amount of metal ions adsorbed by
PANMW-PAR fibers at equilibrium was determined using the following
equation
(Co − Ce) × V
qe =
m (2)
where qe is the saturated adsorption amount of PANMW-PAR fibers,
Ce and C0 denote the concentrations of metal ions before and after
adsorption, respectively, V indicates the volume of adsorption
solution, and m refers to the mass of PANMW-PAR fibers placed
into the solution.
factors is considered to be A3B3C3D2: fiber weight measures 3
g, reaction time totals 50 min, temperature reaches 115 °C,
and ratio of EDA/water (V:V) is 2:1. On the other hand, the
value of R demonstrates the significance of the factor’s
influence; a higher R value indicates a more significant impact.
The ratio of EDA/water (V:V) is the most influential factor,
followed by fiber weight, reaction time, and temperature. To
test the optimized parameters, triplicate experiments were
conducted under A3B3C3D2, and an average of 43.67% GP was
obtained. To the best of our knowledge, faster synthesis time
(50 min) and improved GP (43.67%) are thus far the best
amination results reported in the literature,38,39 confirming the
superior advantage of the MW-assisted method over conven-
tional heating.
Influences of Different Solvent on PAR Functionality.
Solvent type plays an important role in MW adsorption and
rapid heating, thereby further affecting functionality.32,40
Under the MW-assisted method, the ability to convert
electromagnetic energy into heat was measured using a loss
factor named the dielectric loss tangent (tan δ). Different
solvents are generally categorized into three types according to
their high (tan δ > 0.5), medium (tan δ = 0.1−0.5), and low
(tan δ < 0.1) absorbing properties.41 Water is the most

■
RESULTS AND DISCUSSION
Synthesis of PANMW-PAR Fibers under MW Irradi-
ation. Orthogonal Experiment of the Amination Process. In
our previous research studies, the MW-assisted method has
been proven to be a highly efficient approach for surface
modification of PANF fibers.36,37 According to Scheme 1, the
extent of amination significantly affects PAR modification.
Thus, to optimize reaction conditions in terms of grafting rate,
nine experiments were performed according to the L9 (34)
orthogonal matrix. Table 2 summarizes the corresponding GP,
Ki, kj, and R of each factor. Results showed that the range of
GP varied from 7.449% to 39.05%. Higher values of kj
demonstrate that the corresponding levels have more
significant effect on GP. Therefore, the best level for the four
1161
frequently used solvent for PANF modification but is defined
as a medium MW adsorber with tan δ = 0.123. Thus, the effect
of high-loss-factor solvents, such as ethylene glycol (1.350) and
ethanol (0.941), was used for immobilization of PAR onto
PANMW-EDA fibers with the MW-assisted method. As
depicted in Figure 1, the maximum grafting rate in ethylene
glycol solution reached 31.95%, whereas that for ethanol and
water totaled 28.5% and 33.8%, respectively. Although the
discrepancy of grafting rates for these three solvents is
relatively small, reaction time in ethylene glycol dramatically
reduced to 0.3 h compared with 3 h in ethanol and 9 h in
water. Temperature increased from 24 to 160 °C in ethylene
glycol in 32 s. These findings can be explained by the role of
ethylene glycol as a highly efficient MW adsorber and by
instant heating. The rapid increase in temperature is assumed
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Figure 1. Effect of different solvents for PAR functionality as a
function of time.
to effectively decrease the side effects and to improve reaction
efficiency of PANMW-fibers.42
Characterization of PANMW-PAR Fibers. As shown in
Figure 2, peaks at wavenumbers 2946, 2243, and 1680 cm−1
Figure 2. FTIR spectra of (a) pristine PANF, (b) PANMW-EDA fibers,
and (c) PANMW-PAR fibers.
were observed, and they are allocated to the characteristic
adsorptions of the −CH2−, −CN, and (C(O)−OCH3)
groups in the PANF framework, respectively.24,43 After
amination, the stretching vibration at 2243 cm−1 decreased
along with the appearance of updated peaks at 1640, 1560, and
986 cm−1, which correspond to stretching vibrations of −C
N, −N−H, and −C−N groups, respectively.25 Mannich
reaction occurred among −NH2, HCHO, and α-H within
PAR molecules, and the disappearance of the peaks at 3358
and 3292 cm−1 indicates the participation of primary amines in
the reaction.35 The new bands at 3378 and 1732 cm−1 are
attributed to phenolic hydroxyl and −NN− groups,
respectively.44,45 The associated peaks were also observed at
1200 cm−1, and −OH and −C−O groups were assumed to
exist.46−48 These results confirm that PAR has been
successfully immobilized onto PANF. In addition, XPS results
in Figure S2 further convinced the anchoring of PAR onto
PAN fibers.
Application for Colorimetric Detection of Heavy
Metal Ions. Colorimetric Detection of Different Metal
Ions. As shown in Figure S3(a), after adding into different
metal ion solutions with an identical concentration of 50 mg/
L, the fibers exhibited a remarkable red-to-black color change
for Hg2+, Pb2+, Cu2+, and Ni2+ ions and a red-to-purple-red
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change for Cr3+, Cd2+, and Zn2+. Notably, the light metal ions,
including Ca2+, Mg2+, and Al3+, presented no color change,
indicating the absence of interference of light metal ions in the
PANMW-PAR fibers. When the concentration of metal ions
decreased to 5 mg/L, a red-to-black color change was only
observed in the presence of Hg2+ solution (Figure S3(b)),
indicating the superior visual selectivity of PANMW-PAR fibers
for Hg2+ ion at low concentrations.
Furthermore, as presented in Figure 3, UV−vis spectra
results showed that PANMW-PAR fibers exhibited characteristic
Figure 3. UV−vis adsorption spectra of PANMW-PAR fibers after
being immersed into different metal ions solution.
peak at 420 nm, which is the typical adsorption band of PAR
molecules.46 With the addition of Ca2+, Mg2+, Al3+, and Cr3+,
no significant effects on the absorbance at A420 nm can be
detected, indicating that no interaction occurred between
PANMW-PAR fiber and these ions. With the addition of Cd2+,
Zn2+, Hg2+, Pb2+, Cu2+, and Ni2+ ions, the adsorption band
shifted to 520 nm. This observation can be explained by the
coordination effect between the unoccupied orbitals of heavy
metal ions and the azo nitrogen and ortho-hydroxyl group
within PAR molecules.57
Additionally, the colorimetric selectively result in the SI
demonstrates that PANMW-PAR fibers act as outstanding visual
sensors for selective recognition of Hg2+ at low concentrations.
Effect of pH. Given the hydrolysis of Cu2+ and Pb2+ under
basic condition, the pH was then set from 2 to 10 for Hg2+ and
Ni2+ and from 2 to 6 for Cu2+ and Pb2+. As depicted in Figure
4a, the PANMW-PAR fibers exhibited a consistent red-to-black
change for Hg2+, indicating that the colorimetric behavior
remained unaffected under pH ranging from 2 to 10. This
demonstrated that PANMW-PAR fibers possess a high potential
application feature for Hg2+ recognition on account of its wide
pH range adaptability. Comparatively, the red-to-black color
alteration can be only visually observed at pH values of 6−7,
4−6, and 5 for Cu2+, Pb2+, and Ni2+, respectively, as shown in
Figure S5 in SI. At pH 3, the color of PANMW-PAR fibers
converted solely from red to black in the presence of Hg2+,
while no color change was visualized for functionalized fibers
when subject to other heavy metal ions. Thus, high selectivity
for detection of Hg2+ can also be achieved in strongly acidic
solutions.
Detection Kinetics. As shown in Figure 5, the uptake rate of
Hg2+ increased rapidly in 1 min and reached the maximum in 5
min, which is in accordance with the pictures by addition of
10−2 mol/L Hg2+ that led to an instantaneous (5 s) red-to-
black color change of PANMW-PAR fibers, as presented in
Figure S6 (a) in SI. Also, the color remained unchanged within
60 min. This observation indicates the superior visual
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Figure 4. Optical images of PANMW-PAR fibers for (a) Hg2+ as a function of pH value from 2 to 12 with a concentration at 10 mg/L and (b)
various metal ions at pH 3 with a concentration of 50 mg/L.

good agreement with the kinetics of the absorbance for Cu2+,

Figure 5. Curves of UV−vis adsorption spectra at 520 nm as a
function of time. Note that the pH of the solution during the
experiment is set without further adjustment.
detection efficiency of PANMW-PAR fibers toward Hg2+.
Comparatively, as shown in Figure S6(b), S6(c), and S6(d),
the fibers immersed in Cu2+, Pb2+, and Ni2+ showed
distinguished color changes at 10, 30, and 60 min, respectively.
The corresponding digital images shown in Figure S6 present
Pb2+, and Ni2+ presented in Figure 5. The fast detection
kinetics toward Hg2+ may be due to the strong affinity between
PANMW-PAR fibers and Hg2+.
Effect of Concentration. Given the good detection ability of
PAN MW -PAR fibers toward Hg 2+ , the effect of Hg 2+
concentration was evaluated by immersing PANMW-PAR fibers
into a sequence of Hg2+ solutions within the range from 0.5 to
20 mg/L. Optical images of PANMW-PAR fibers for various
concentrations of Hg2+ were obtained, as shown in Figure 6a.
At low concentration, the fibers displayed a dark purple color,
and with the increase of Hg2+ concentration, the color of fibers
transformed into black starting from 4 mg/L. In the meantime,
as shown in Figure 6b, the absorbance intensity at 520 nm of
PANMW-PAR fibers after colorimetric reaction increased
gradually with increasing Hg2+ concentration. The absorption
intensity and Hg2+ concentration range from 0.5 to 20 mg/L
presented a linear relationship with an R2 value of 0.9748, as
shown in Figure 6c. Thus, Hg2+ ions in aqueous solution, at a
concentration of 0.5−20 mg/L, can be precisely recognized
with PANMW-PAR fibers with an association constant of 0.007

Figure 6. (a) Optical images, (b) UV−vis adsorption spectra, and (c) adsorption intensity at 520 nm of PANMW-PAR fibers after interacting with
various concentration of Hg2+. Note that the pH of the solution during the experiment is set without further adjustment.

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Figure 7. (a) pHpzc determination of PANMW-EDA and PANMW-PAR fibers, and (b) effect of initial pH value on the adsorption of Hg2+, Cu2+,
Pb2+, and Ni2+ onto PANMW-PAR fibers.
Figure 8. Adsorption kinetics curves of Hg2+, Cu2+, Pb2+, and Ni2+ onto PANMW-PAR fibers at room temperature.
L/mg. Spectrometric detection limit (DL) of Hg2+ for
visualized fibers was calculated according to the following
equation49
Sb × k
DL =
m (3)
where the value of k is 3, Sb represents the blank standard
deviation, and m refers to the calibration slope of the graph.
The calculated Sb totaled 0.0082% after in 5 continuous
testings, and the calculated DL reached 35 μg/L. Depite this
concentration exceeding the maximum allowance concen-
tration of Hg2+ (2 μg/L) in drinking water permitted by the
U.S. EPA,50 this functionalized fiber can still be used for
visualized detection of Hg2+ in specific wastewater containing a
high concentration of Hg2+; examples of such wastewaters
include electroplating effluent and suddenly Hg2+-polluted
water. In addition, reusability studies of PANMW-PAR fibers in
the SI confirmed the high reversibility of PANMW-PAR fibers
for Hg2+ recognition.
Adsorption Performance Studies. Effect of pH. As
shown in Figure 7a, the obtained pHpzc for PANMW-EDA fibers
equaled 8.3, which is in accordance with the results of previous
reports.51 The pHpzc value for PANMW-PAR fibers totaled 5.7,
and this result shows good agreement with that of PAR, which
is described as a dibasic acid with pKa1 and pKa2 values of 5.6
and 11.9, respectively.52 As shown in Figure 7b, the adsorption
rate increased as the pH value for the four metal ions
increased, and the maximum adsorption amount was reached
at pH = 7, 6, 5, and 6 for Hg2+, Cu2+, Pb2+, and Ni2+ ions,
respectively. This trend may be related to the adsorbent
property of the different species of metal ions. At low acid
concentrations, competition between metal ions and acid was
high, causing a significantly difficult large complex formation.
These repulsion effects became less effective when the pH
value increased. Thus, the uptake amount of metal ions
increased. The pKsp value of metal hydroxides for Ni2+, Pb2+,
Cu2+, and Hg2+ ions measures 14.7, 14.93, 19.32, and 23.7,
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respectively, which indicates the higher accessibility of Ni2+
and Pb2+ to form precipitates with increasing pH. Thus, the
adsorption amount decreased when the pH was higher than 5
for Pb2+ and 6 for Ni2+ and Cu2+. The amount of Hg2+ ions in
the solution varied with increasing pH. More specifically, at
low pH, Hg2+ ions acted as dominating species, thereby
inducing a high electrostatic barrier effect and prohibiting
further affinity to the fiber. When solution pH increased
gradually, the neutral species, such as HgCl2, (HgCl2)2, and
Hg(OH)Cl, were presented primarily.53 These neutral species
overcame the electrostatic barrier and increased adsorption.
However, when solution pH continuously increased, Hg-
(OH)3−, Hg2(OH)2, and Hg(OH)2 species were generated,54
resulting in the electrostatic repulsion from the slightly
negatively charged surface of PANMW-PAR fibers (pHpzc =
5.6). The precipitate formed may also hinder adsorption at
elevated pH levels.54,55 Thus, the optimum pH conditions for
Hg2+, Cu2+, Pb2+, and Ni2+ ions were set at pH values of 7, 6, 5,
and 6, respectively, in further experiments.
Adsorption Kinetics. The adsorption behavior of PANMW-
PAR fibers for heavy metal ion in terms of time is illustrated in
Figure 8, and three adsorption kinetic models were applied for
the interpretation of the process. The adsorption data were
subjected to three commonly used kinetics models.32 Details of
these three models are provided in the SI. Table S1
summarizes the parameters and the correlation coefficient
calculated based on a nonlinear approach. The nonlinear
correlation coefficient R2 values of the pseudo-second-order
model were all higher than 0.99, whereas those values for the
pseudo-first-order and Weber−Morris model had less agree-
ment with adsorption. The qe values calculated from the
pseudo-second-order model for Hg2+ (151.51 mg/g), Cu2+
(94.34 mg/g), Pb2+ (73.53 mg/g), and Ni2+ (66.67 mg/g) are
the closest to the equilibrium capacities obtained from
experiments. Accordingly, adsorption of the four heavy metal
ions onto PANMW-PAR fibers is mainly controlled by a
chemically reactive process. Figure S9 shows the possible
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Figure 9. Adsorption isoterm curves of Hg2+, Cu2+, Pb2+, and Ni2+ onto PANMW-PAR fibers at room temperature.
Figure 10. XPS spectra of (a) wide scan of PANMW-PAR fibers before and after Hg2+, Cu2+, Pb2+, and Ni2+ adsorption, N 1s spectra of PANMW-
PAR fibers before (b) and after (c) Hg2+ adsorption, O 1s spectra of PANMW-PAR fibers before (d) and after (e) Hg2+ adsorption, and (f) detailed
analysis of Hg 4f.
complex structure of PAR with metal ions.56 The adsorption
rate, especially for the early stage, can be indicated by a factor
named H0 (k2q2e ),57 and the calculated initial adsorption rates
H0 followed the order Hg2+ (9.56) > Cu2+ (4.07) > Pb2+ (2.89)
> Ni2+ (2.30) at fixed initial concentration, coinciding with the
affinity order observed previously.
Adsorption Isotherms. Figure 9 shows the adsorption
isotherms of different metal ions into PANMW-PAR fibers. Such
behavior can be simulated by applying the well-established
fundamental isotherm models, including Langmuir, Freundlich,
and Temkin models.38 Details of these three models are
provided in the SI. Table S2 lists the corresponding parameters
of these three models. For all data, the Langmuir model was
followed, with the highest R2 value denoting a homogeneous
adsorption, and the maximum adsorption capacities for Hg2+,
Cu2+, Pb2+, and Ni2+ were 181.2, 116.9, 77.07, and 70.33 mg/g,
respectively. Table S3 lists the metal ion adsorption capacities
of PANMW-PAR fibers and other fibrous adsorbents with
different functional groups. As shown in Table S3, the PANMW-
PAR fibers exhibited a higher adsorption capacity than other
fibrous adsorbents, and with their unique colorimetric
detection ability, PANMW-PAR fibers can still be considered
to show potential in dealing with practical heavy metal
wastewater. Furthermore, as discussed in the SI, the PANMW-
PAR fibers also exhibited good stability on readsorption
efficiency for heavy metals in 10 cycles of reuse.
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Research Article
Adsorption Mechanism. The coordination effect between
PAR and metal ions is widely assumed to lead to the color
change and thus allows the possibility of naked-eye detection.
One metal can form a complex with one, two, or three PAR
molecules. As shown in Figure 10a, after adsorption of Hg2+,
the characteristic peaks of Hg 4f, Hg 4d3, and Hg 4d5
appeared in the spectrum, and the same results were observed
after adsorption of Cu2+, Pb2+, and Ni2+ with the appearance of
Cu 2p, Pb 4f, and Ni 2p peaks, respectively. Occurrence of
these peaks confirmed the capture of metal ions onto PARMW-
PAR fibers. To further interpret the effects between PAR and
metal ions, XPS N 1s and O 1s core-level spectra were
analyzed, and Hg2+ was selected as an example. Compared with
N 1s spectra of PANMW-PAR fibers (Figure 10b), the peak at
398.3 eV, which corresponds to −NN−,58 reduced after
Hg2+ adsorption, and a new peak simultaneously appeared at
400.5 eV (Figure 10c). XPS N 1s results suggest that a
chemical interaction exists in the −NN and −C−N groups
of PANMW-PAR fibers for Hg2+ adsorption. XPS O 1s spectra
of PARMW-PAR fibers in Figure 10d can be assigned to the two
peaks at 531.8 and 532.8 eV for the oxygen in the CO and
−OH groups, respectively. After adsorption of Hg2+, a new
peak appeared at 534.2 eV, and the peak at 532.8 eV was
reduced due to adsorption, as illustrated in Figure 10e. Results
indicate that the hydroxyl groups on the surface of PARMW-
PAR fibers may be involved in adsorption of Hg2+. As
displayed in Figure 10f, XPS Hg 4f spectra can be allocated
DOI: 10.1021/acssuschemeng.8b04760
ACS Sustainable Chem. Eng. 2019, 7, 1159−1168
ACS Sustainable Chemistry & Engineering
into two peaks in 101.5 and 104.8 eV, which are assigned to
Hg 4f 7/2 and Hg 4f 5/2, respectively. These results suggest the
participation of pyridine nitrogen atom, azo nitrogen, and
ortho-hydroxyl group in binding Hg2+, agreeing with previous
reports in the literature.59,60
■ CONCLUSION
In this work, PANMW-PAR fibers were synthesized for
simultaneous detection and removal of heavy metal ions
from water. MW irradiation was introduced for the synthesis of
PANMW-PAR fibers instead of conventional heating. The
modification time was dramatically shortened, whereas the
grating rate significantly increased. The type of solvent was
found to be important for rapid and highly efficient
functionalization of the fibers. Ethylene glycol was selected
as the optimum solvent due to its superior MW adsorption
ability. FT-IR and XPS analysis findings demonstrated the
successful immobilization of PAR onto PANF fibers. On the
basis of the strong affinity between PANMW-PAR fibers and
heavy metal ions, including Hg2+, Cu2+, Pb2+, and Ni2+, a red-
to-black color change was observed, whereas no response was
observed with the existence of light metal ions, such as Ca2+,
Mg2+, and Al3+, illustrating the excellent selectivity of PANMW-
PAR fibers for heavy metal ions. PANMW-PAR fibers exhibited
a selective colorimetric effect for Hg2+ at pH = 3 with a low
naked-eye detection limit of 35 μg/L, whereas a distinct color
change (5 s) was observed at 10−2 mol/L Hg2+ solution.
Pseudo-second-order kinetics present the best-fitting result,
implying the chemisorption effect for heavy metal ions. The
adsorption isotherm data followed the Langmuir isotherm
model, and the adsorption capacities can reach up to 181.2,
116.9, 77.07, and 70.33 mg/g for Hg2+, Cu2+, Pb2+, and Ni2+,
respectively. XPS data provided direct evidence for the
interaction of metal ions with the PAR moiety, underscoring
the role of nitrogen and oxygen for the affinity process. The
dual-function fibers also exhibited good stability on optical
detection and readsorption efficiency for heavy metals in 10
cycles of reuse. Therefore, the synthesized materials, which can
detect low concentrations and adsorb heavy metal ions
efficiently, can significantly benefit environmental remediation
efforts.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.8b04760.
Feature of the MW reactor and XPS analyses of PAN
fibers before and after modification; digital photos of
PANMW-PAR fibers in the presence of various metal ions
as a function of different concentrations, times, and pHs;
optical images, UV−vis adsorption spectra, and read-
sorption efficiency of functional fibers after 10 successive
cycles of usage and possible complex structure with
heavy metal ions (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: gszhanghit@gmail.com. Tel.: +86-451-82933538.
*E-mail: pwang73@vip.sina.com. Tel.: +86-451-86283557.
ORCID
Guangshan Zhang: 0000-0002-7190-415X
1166
Research Article
Peng Wang: 0000-0003-4465-6207
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (51678185 and 51779066), State Key
Laboratory of Urban Water Resource and Environment
(Harbin Institute of Technology) (2017DX11), and Techno-
logical Innovation Talent Special fund of Harbin, China
(2016RAQXJ175).
■
REFERENCES
(1) RoyChowdhury, A.; Datta, R.; Sarkar, D. Heavy Metal Pollution
and Remediation. Green Chemistry; Elsevier: 2018; Chapter 3.10, pp
359−373.
(2) Xu, G.; Xie, Y.; Cao, J.; Tao, M.; Zhang, W. Q. Highly Selective
and Efficient Chelating Fiber Functionalized by Bis(2-Pyridylmethyl)-
Amino Group for Heavy Metal Ions. Polym. Chem. 2016, 7 (23),
3874−3883.
(3) Wang, X.; Lv, P.; Zou, H.; Li, Y.; Li, X.; Liao, Y. Synthesis of
Poly(2-Aminothiazole) for Selective Removal of Hg(II) in Aqueous
Solutions. Ind. Eng. Chem. Res. 2016, 55 (17), 4911−4918.
(4) Luo, C.; Wang, J.; Jia, P.; Liu, Y.; An, J.; Cao, B.; Pan, K.
Hierarchically Structured Polyacrylonitrile Nanofiber Mat as Highly
Efficient Lead Adsorbent for Water Treatment. Chem. Eng. J. 2015,
262, 775−784.
(5) Akhavan, B.; Jarvis, K.; Majewski, P. Plasma Polymer-
Functionalized Silica Particles for Heavy Metals Removal. ACS
Appl. Mater. Interfaces 2015, 7 (7), 4265−4274.
(6) Chen, L.; Zhou, S.; Shi, Y.; Wang, C.; Li, B.; Li, Y.; Wu, S. Heavy
Metals in Food Crops, Soil, and Water in the Lihe River Watershed of
the Taihu Region and Their Potential Health Risks When Ingested.
Sci. Total Environ. 2018, 615, 141−149.
(7) Matlock, M. M.; Howerton, B. S.; Atwood, D. A. Chemical
Precipitation of Heavy Metals from Acid Mine Drainage. Water Res.
2002, 36 (19), 4757−4764.
(8) Meunier, N.; Drogui, P.; Montané, C.; Hausler, R.; Mercier, G.;
Blais, J.-F. Comparison between Electrocoagulation and Chemical
Precipitation for Metals Removal from Acidic Soil Leachate. J.
Hazard. Mater. 2006, 137 (1), 581−590.
(9) Oehmen, A.; Viegas, R.; Velizarov, S.; Reis, M. A. M.; Crespo, J.
G. Removal of Heavy Metals from Drinking Water Supplies through
the Ion Exchange Membrane Bioreactor. Desalination 2006, 199 (1),
405−407.
(10) Azarudeen, R. S.; Subha, R.; Jeyakumar, D.; Burkanudeen, A. R.
Batch Separation Studies for the Removal of Heavy Metal Ions Using
a Chelating Terpolymer: Synthesis, Characterization and Isotherm
Models. Sep. Purif. Technol. 2013, 116, 366−377.
(11) Li, A.; Zhou, C.; Liu, Z.; Xu, X.; Zhou, Y.; Zhou, D.; Tang, Y.;
Ma, F.; Rittmann, B. E. Direct Solid-State Evidence of H2-Induced
Partial U(VI) Reduction Concomitant with Adsorption by Extrac-
ellular Polymeric Substances (EPS). Biotechnol. Bioeng. 2018, 115 (7),
1685−1693.
(12) Gao, J.; Sun, S. P.; Zhu, W.-P.; Chung, T. S. Chelating Polymer
Modified P84 Nanofiltration (NF) Hollow Fiber Membranes for
High Efficient Heavy Metal Removal. Water Res. 2014, 63, 252−261.
(13) Bai, L.; Liang, H.; Crittenden, J.; Qu, F.; Ding, A.; Ma, J.; Du,
X.; Guo, S.; Li, G. Surface Modification of UF Membranes with
Functionalized MWCNTs to Control Membrane Fouling by NOM
Fractions. J. Membr. Sci. 2015, 492, 400−411.
(14) Nidheesh, P. V.; Singh, T. S. A. Arsenic Removal by
Electrocoagulation Process: Recent Trends and Removal Mechanism.
Chemosphere 2017, 181, 418−432.
(15) Hu, S.; Li, D.; Huang, C.; Sun, D.; Yuan, X. A Continuous
Electrocoagulation System with PH Auto-Adjusting by Endogenous
DOI: 10.1021/acssuschemeng.8b04760
ACS Sustainable Chem. Eng. 2019, 7, 1159−1168
ACS Sustainable Chemistry & Engineering
Products to Treat Cr(VI)-Contaminated Soil Flushing Solution. Sep.
Purif. Technol. 2017, 189, 213−219.
(16) Xu, J.; Cao, Z.; Zhang, Y.; Yuan, Z.; Lou, Z.; Xu, X.; Wang, X. A
Review of Functionalized Carbon Nanotubes and Graphene for
Heavy Metal Adsorption from Water: Preparation, Application, and
Mechanism. Chemosphere 2018, 195, 351−364.
(17) Efome, J. E.; Rana, D.; Matsuura, T.; Lan, C. Q. Experiment
and Modeling for Flux and Permeate Concentration of Heavy Metal
Ion in Adsorptive Membrane Filtration Using a Metal-Organic
Framework Incorporated Nanofibrous Membrane. Chem. Eng. J.
2018, 352, 737−744.
(18) Efome, J. E.; Rana, D.; Matsuura, T.; Lan, C. Q. Insight Studies
on Metal-Organic Framework Nanofibrous Membrane Adsorption
and Activation for Heavy Metal Ions Removal from Aqueous
Solution. ACS Appl. Mater. Interfaces 2018, 10 (22), 18619−18629.
(19) Efome, J. E.; Rana, D.; Matsuura, T.; Lan, C. Q. Metal−
Organic Frameworks Supported on Nanofibers to Remove Heavy
Metals. J. Mater. Chem. A 2018, 6 (10), 4550−4555.
(20) Sherlala, A. I. A.; Raman, A. A. A.; Bello, M. M.; Asghar, A. A
Review of the Applications of Organo-Functionalized Magnetic
Graphene Oxide Nanocomposites for Heavy Metal Adsorption.
Chemosphere 2018, 193, 1004−1017.
(21) Fakhre, N. A.; Ibrahim, B. M. The Use of New Chemically
Modified Cellulose for Heavy Metal Ion Adsorption. J. Hazard. Mater.
2018, 343, 324−331.
(22) Yıldız, M.; Demir, N.; Ü nver, H.; Sahiner, N. Synthesis,
Characterization, and Application of a Novel Water-Soluble
Polyethyleneimine-Based Schiff Base Colorimetric Chemosensor for
Metal Cations and Biological Activity. Sens. Actuators, B 2017, 252,
55−61.
(23) Kaur, B.; Kaur, N.; Kumar, S. Colorimetric Metal Ion Sensors −
A Comprehensive Review of the Years 2011−2016. Coord. Chem. Rev.
2018, 358, 13−69.
(24) Li, Y.; Wen, Y.; Wang, L.; He, J.; Al Deyab, S. S.; El Newehy,
M.; Yu, J.; Ding, B. Simultaneous Visual Detection and Removal of
Lead Ions with Pyromellitic Dianhydride-Grafted Cellulose Nano-
fibrous Membranes. J. Mater. Chem. A 2015, 3 (35), 18180−18189.
(25) Kumari, S.; Chauhan, G. S. New Cellulose−Lysine Schiff-Base-
Based Sensor−Adsorbent for Mercury Ions. ACS Appl. Mater.
Interfaces 2014, 6 (8), 5908−5917.
(26) Deng, S.; Bai, R. Removal of Trivalent and Hexavalent
Chromium with Aminated Polyacrylonitrile Fibers: Performance and
Mechanisms. Water Res. 2004, 38 (9), 2424−2432.
(27) Zhao, R.; Li, X.; Sun, B.; Li, Y.; Li, Y.; Yang, R.; Wang, C.
Branched Polyethylenimine Grafted Electrospun Polyacrylonitrile
Fiber Membrane: A Novel and Effective Adsorbent for Cr(VI)
Remediation in Wastewater. J. Mater. Chem. A 2017, 5 (3), 1133−
1144.
(28) Ndayambaje, G.; Laatikainen, K.; Laatikainen, M.; Beukes, E.;
Fatoba, O.; van der Walt, N.; Petrik, L.; Sainio, T. Adsorption of
Nickel(II) on Polyacrylonitrile Nanofiber Modified with 2-(2′-
Pyridyl)Imidazole. Chem. Eng. J. 2016, 284, 1106−1116.
(29) Alcaraz-Espinoza, J. J.; Chávez-Guajardo, A. E.; Medina-Llamas,
J. C.; Andrade, C. A. S.; de Melo, C. P. Hierarchical Composite
Polyaniline−(Electrospun Polystyrene) Fibers Applied to Heavy
Metal Remediation. ACS Appl. Mater. Interfaces 2015, 7 (13),
7231−7240.
(30) Li, X.; Zhang, C.; Zhao, R.; Lu, X.; Xu, X.; Jia, X.; Wang, C.; Li,
L. Efficient Adsorption of Gold Ions from Aqueous Systems with
Thioamide-Group Chelating Nanofiber Membranes. Chem. Eng. J.
2013, 229, 420−428.
(31) Xing, X.; Yang, H.; Tao, M.; Zhang, W. An Overwhelmingly
Selective Colorimetric Sensor for Ag+ Using a Simple Modified
Polyacrylonitrile Fiber. J. Hazard. Mater. 2015, 297, 207−216.
(32) Liu, X.; Liu, X.; Tao, M.; Zhang, W. A Highly Selective and
Sensitive Recyclable Colorimetric Hg Sensor Based on the Porphyrin-
Functionalized Polyacrylonitrile Fiber. J. Mater. Chem. A 2015, 3 (25),
13254−13262.
1167
Research Article
(33) Li, S.; Zhang, G.; Wang, P.; Zheng, H.; Zheng, Y. Microwave-
enhanced Mn-Fenton process for the removal of BPA in water. Chem.
Eng. J. 2016, 294, 371−379.
(34) Schwenke, A. M.; Hoeppener, S.; Schubert, U. S. Microwave
Synthesis of Carbon Nanofibers − the Influence of MW Irradiation
Power, Time, and the Amount of Catalyst. J. Mater. Chem. A 2015, 3
(47), 23778−23787.
(35) de la Hoz, A.; Díaz-Ortiz, Á .; Moreno, A. Microwaves in
Organic Synthesis. Thermal and Non-Thermal Microwave Effects.
Chem. Soc. Rev. 2005, 34 (2), 164−178.
(36) Liu, T.; Li, G.; Zhang, N.; Chen, Y. An Inorganic−organic
Hybrid Optical Sensor for Heavy Metal Ion Detection Based on
Immobilizing 4-(2-Pyridylazo)-Resorcinol on Functionalized HMS. J.
Hazard. Mater. 2012, 201−202, 155−161.
(37) Hua, Z.; Yang, B.; Chen, W.; Bai, X.; Xu, Q.; Gu, H. Surface
Functionalized Magnetic PVA Microspheres for Rapid Naked-Eye
Recognizing of Copper(II) Ions in Aqueous Solutions. Appl. Surf. Sci.
2014, 317, 226−235.
(38) Deng, S.; Zhang, G.; Liang, S.; Wang, P. Microwave Assisted
Preparation of Thio-Functionalized Polyacrylonitrile Fiber for the
Selective and Enhanced Adsorption of Mercury and Cadmium from
Water. ACS Sustainable Chem. Eng. 2017, 5 (7), 6054−6063.
(39) Deng, S.; Zhang, G.; Chen, S.; Xue, Y.; Du, Z.; Wang, P. Rapid
and Effective Preparation of a HPEI Modified Biosorbent Based on
Cellulose Fiber with a Microwave Irradiation Method for Enhanced
Arsenic Removal in Water. J. Mater. Chem. A 2016, 4 (41), 15851−
15860.
(40) Kiani, G. R.; Sheikhloie, H.; Arsalani, N. Heavy Metal Ion
Removal from Aqueous Solutions by Functionalized Polyacrylonitrile.
Desalination 2011, 269 (1−3), 266−270.
(41) Wang, N.; Wang, P. Study and Application Status of Microwave
in Organic Wastewater Treatment − A Review. Chem. Eng. J. 2016,
283, 193−214.
(42) Hu, L.; Zhang, G.; Wang, Q.; Sun, Y.; Liu, M.; Wang, P. Facile
Synthesis of Novel Co3O4-Bi2O3 Catalysts and Their Catalytic
Activity on Bisphenol A by Peroxymonosulfate Activation. Chem.
Eng. J. 2017, 326, 1095−1104.
(43) Rathi, A. K.; Gawande, M. B.; Zboril, R.; Varma, R. S.
Microwave-Assisted Synthesis − Catalytic Applications in Aqueous
Media. Coord. Chem. Rev. 2015, 291, 68−94.
(44) Deng, S.; Bai; Chen, J. P. Aminated Polyacrylonitrile Fibers for
Lead and Copper Removal. Langmuir 2003, 19 (12), 5058−5064.
(45) Deng, S.; Bai, R.; Chen, J. P. Behaviors and Mechanisms of
Copper Adsorption on Hydrolyzed Polyacrylonitrile Fibers. J. Colloid
Interface Sci. 2003, 260 (2), 265−272.
(46) Deng, S.; Bai, R. Adsorption and Desorption of Humic Acid on
Aminated Polyacrylonitrile Fibers. J. Colloid Interface Sci. 2004, 280
(1), 36−43.
(47) Deng, S.; Wang, P.; Zhang, G.; Dou, Y. Polyacrylonitrile-Based
Fiber Modified with Thiosemicarbazide by Microwave Irradiation and
Its Adsorption Behavior for Cd(II) and Pb(II). J. Hazard. Mater.
2016, 307, 64−72.
(48) Zhao, R.; Li, Y.; Li, X.; Li, Y.; Sun, B.; Chao, S.; Wang, C. Facile
Hydrothermal Synthesis of Branched Polyethylenimine Grafted
Electrospun Polyacrylonitrile Fiber Membrane as a Highly Efficient
and Reusable Bilirubin Adsorbent in Hemoperfusion. J. Colloid
Interface Sci. 2018, 514, 675−685.
(49) Yusof, N. A.; Ahmad, M. Development of a Flow-through
Optosensor for Determination of Co(II). Spectrochim. Acta, Part A
2008, 69 (2), 413−418.
(50) Jeronimo, P. A.; Araujo, A.; Montenegro, M. C. S. M.; Pasquini,
C.; Raimundo, I. Direct Determination of Copper in Urine Using a
Sol-Gel Optical Sensor Coupled to a Multicommutated Flow System.
Anal. Bioanal. Chem. 2004, 380 (1), 108−114.
(51) ElSafty, S. A.; Ismail, A. A.; Matsunaga, H.; Nanjo, H.;
Mizukami, F. Uniformly Mesocaged Cubic Fd3m Monoliths as Modal
Carriers for Optical Chemosensors. J. Phys. Chem. C 2008, 112 (13),
4825−4835.
DOI: 10.1021/acssuschemeng.8b04760
ACS Sustainable Chem. Eng. 2019, 7, 1159−1168
ACS Sustainable Chemistry & Engineering Research Article

(52) Zhu, H.; Fan, J.; Chen, H.; Tang, Z.; Wang, G.; Fu, N. An
EDTA Promoted Coordination Induced Disaggregation for Specific
Hg2+ Detection. Dyes Pigm. 2015, 113, 181−188.
(53) Zhao, R.; Li, X.; Sun, B.; Shen, M.; Tan, X.; Ding, Y.; Jiang, Z.;
Wang, C. Preparation of Phosphorylated Polyacrylonitrile-Based
Nanofiber Mat and Its Application for Heavy Metal Ion Removal.
Chem. Eng. J. 2015, 268, 290−299.
(54) Ghasemi, J.; Peyman, H.; Meloun, M. Study of Complex
Formation between 4-(2-Pyridylazo) Resorcinol and Al3+Fe3+Zn2+
and Cd2+ Ions in an Aqueous Solution at 0.1 M Ionic Strength. J.
Chem. Eng. Data 2007, 52 (4), 1171−1178.
(55) Saha, D.; Barakat, S.; Van Bramer, S. E.; Nelson, K. A.; Hensley,
D. K.; Chen, J. Noncompetitive and Competitive Adsorption of
Heavy Metals in Sulfur-Functionalized Ordered Mesoporous Carbon.
ACS Appl. Mater. Interfaces 2016, 8 (49), 34132−34142.
(56) Li, L.; Liu, F.; Jing, X.; Ling, P.; Li, A. Displacement
Mechanism of Binary Competitive Adsorption for Aqueous Divalent
Metal Ions onto a Novel IDA-Chelating Resin: Isotherm and Kinetic
Modeling. Water Res. 2011, 45 (3), 1177−1188.
(57) Zhou, X.; Nie, J.; Du, B. 4-(2-Pyridylazo)-Resorcinol
Functionalized Thermosensitive Ionic Microgels for Optical Detec-
tion of Heavy Metal Ions at Nanomolar Level. ACS Appl. Mater.
Interfaces 2015, 7 (39), 21966−21974.
(58) Luo, X.; Yuan, J.; Liu, Y.; Liu, C.; Zhu, X.; Dai, X.; Ma, Z.;
Wang, F. Improved Solid-Phase Synthesis of Phosphorylated
Cellulose Microsphere Adsorbents for Highly Effective Pb2+ Removal
from Water: Batch and Fixed-Bed Column Performance and
Adsorption Mechanism. ACS Sustainable Chem. Eng. 2017, 5 (6),
5108−5117.
(59) Lee, S.; Kang, S.; Eom, M. S.; Han, M. S. Colorimetric Assay for
β-Lactamase Activity Using Cocktail of Penicillin and 4-(2-
Pyridylazo)Resorcinol (PAR)−2Hg2+ Complex. Dyes Pigm. 2017,
137, 518−522.
(60) Vyshcherevich, I. V.; Kalinichenko, I. E. Photometric
Determination in Drinking Water of Cobalt and Nickel with 4-(2-
Pyridylazo)-Resorcinol. J. Water Chem. Technol. 2010, 32 (1), 33−38.

1168 DOI: 10.1021/acssuschemeng.8b04760

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