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Selective removal of cationic micro-pollutants

Cite this: RSC Adv., 2017, 7, 25969
using disulfide-linked network structures†
Mehmet Sahin Atas,a Sami Dursun,a Hasan Akyildiz,a Murat Citir, b

Cafer T. Yavuz *c and Mustafa Selman Yavuz *a

Micropollutants are found in all water sources, even after thorough treatments that include membrane
filtration. New ones emerge as complex molecules are continuously produced and discarded after used.
Treatment methods and sorbent designs are mainly based on non-specific interactions and, therefore,
have been elusive. Here, we developed swellable covalent organic polymers (COP) with great affinity
towards micropollutants, such as textile industry dyes. Surprisingly, only cationic dyes in aqueous
solution were selectively and completely removed. Studies of the COPs surfaces led to a gating capture,
where negatively charged layer attracts cationic dyes and moves them inside the swollen gel through
diffusive and hydrophobic interaction of the hydrocarbon fragments. Despite its larger molecular size,
crystal violet has been taken the most, 13.4 mg g
1, surpassing all competing sorbents. The maximum
Received 28th April 2017
Accepted 3rd May 2017
adsorption capacity increased from 12.4 to 14.6 mg and from 8.9 to 11.4 mg when the temperature of
dye solution was increased from 20 to 70  C. The results indicated that disulfide-linked COPs are
DOI: 10.1039/c7ra04775d
attractive candidates for selectively eliminating cationic dyes from industrial wastewater due to
rsc.li/rsc-advances exceptional swelling behaviour, low-cost and easy synthesis.

are affected by the contaminant induced inhibition of the

Introduction photosynthetic activity.8
Micropollutants are highly water-soluble, oen charged, organic In recent years, a number of techniques were employed for
molecules that are increasingly found in ground and surface the removal of organic pollutants from effluents, including
water.1,2 These organic molecules mainly come from chemical precipitation, membrane ltration, coagulation, ion exchange,
and pharmaceutical industries. Although safety protocols are in adsorption and chemical oxidation.9–15 Among these methods,
place for newly discovered molecules and their environmental adsorption is one of the promising techniques,16–19 mainly due
fate, there are still many unknowns, especially if they undergo to the effective procedure, operational simplicity, low cost and
chemical transformations like oxidation. Conventional sorbents low energy requirements.1 The most widely used adsorbents
like activated carbon suffer from low kinetics and specicity include mesoporous silica,20 organoclays,21 powdered activated
when it comes to extremely hydrophilic micropollutants.2 sludge,22 activated carbon,23 magnetic nanoparticles,24,25
Among the leading sources for micropollutants (Table S1 in zeolite,26 molecular sieves,27,28 activated aluminium oxide29 and
ESI†), industrial use of synthetic dyes has increased consider- porous polymers.30–34 Recently, we have shown that a uori-
ably over the last few decades, particularly in textiles, plastics nated porous polymer can separate water-soluble organic
and papers.3–7 Textile industry is the most prominent where molecules based on their sizes and charges.2
effluents containing large amounts of dye residue have to be Network polymers have been increasingly studied for their
treated before being discharged into wastewater streams. If not tunable functionalities, controllable pore geometries and wide
done properly, water pollution with toxic dyes, metal ions and range of applications.35–42 Although conventional polymers and
organic contaminants pose serious environmental hazards, their derivatives, such as poly(acrylic acid),43 cellulose,44 carbo-
especially for aquatic biosystems, where symbiotic processes naceous materials,45,46 poly(orthocarbonate),47 microporous poly-
mers,48,49 poly(lactic acid),50 polyaniline,51–53 were used as
a
superabsorbents to remove oils, metal ions, toxic dyes and organic
Metallurgy and Materials Engineering Department, Selcuk University, Konya, Turkey.
solvents from water, some of these materials were synthesized by
E-mail: [email protected]
b
Materials Science and Nanotechnology Engineering, Abdullah Gül University,
using transition metal catalysts and sometimes at high tempera-
Melikgazi 38039, Kayseri, Turkey tures.54 Therefore, new, low cost and effective adsorbents are
c
Graduate School of EEWS, Korea Advanced Institute of Science and Technology always needed. One particular challenge is that high selectivity
(KAIST), Daejeon, 34141 Republic of Korea. E-mail: [email protected] requires targeted chemistry, and such control on chemical
† Electronic supplementary information (ESI) available. See DOI: architecture brings additional costs in material production.41
10.1039/c7ra04775d

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RSC Advances Paper

Covalent Organic Polymers (COPs) are highly stable and using an incubator shaker. Samples were placed in an incubator
inexpensive solids41,55 that are oen made from commercially shaker (ZHWY-200B, Labwit, Shanghai, China), which was set at
available monomers with simple chemical transformations. In a speed of 150 rpm and temperature of 30  C.
this study, we used two inexpensive disulde-linked covalent In a typical adsorption study, 100 mg of COPs was added to
organic polymers, COP-65 and COP-66, for selective dye uptake. a 3 mL of an aqueous micropollutant solution (500 mg L
1) at
Surprisingly, only cationic dyes were captured and the capac- room temperature. Aer mixing by the shaker at 200 rpm for
ities did not follow simple surface monolayer coverage. These 24 h, the COPs were removed from the solution and supernatant
COPs were generated through disulde linkages (–S–S–) by easy was analysed by UV-Vis. For example, the adsorbed amount of
oxidative coupling under catalyst-free mild conditions. CV dye was calculated from the difference between the
Adsorption and kinetics of textile dye removal from aqueous concentrations of stock CV dye solution and the supernatant CV
solutions were analysed with respect to the initial dye concen- solution by UV-Vis spectrophotometry at the wavelength of
tration, temperature, pH and sorbent dosage. Our ndings 594 nm. Other cationic dyes MB (668 nm) and RB (554 nm), and
point to signicant potential for swellable polymers in effective anionic dyes as AY (374 nm), MO (463 nm) and OG (481 nm)
water treatment needs. were analysed similarly.

Experimental pH variation

Materials The effect of the initial pH on the percentage removal of CV, MB

and RB through adsorption onto COPs from aqueous dye
Trimethylolpropane tris(3-mercaptopropionate) (98%, 3SH) solution was studied. In that order, the experiments were con-
and pentaerythritol tetrakis(3-mercaptopropionate) (98%, 4SH) ducted at various pH values, ranging from 2.0 to 10.0 with
were obtained from Sigma-Aldrich. Dimethyl sulfoxide (99.5%, a 500 mg L
1 initial dye concentration and 100 mg of COPs
DMSO), tetrahydrofuran (98%, THF) and methanol (98%, (adsorbent) at room temperature for 24 h. The pH was adjusted
MeOH) were purchased from Merck Chemical Company. with 0.1 M hydrochloric acid (HCl) or 0.1 M sodium hydroxide
Cationic dye Rhodamine B (RB) was obtained from Alfa Aesar, (NaOH) by using a pH meter.
Methylene Blue (MB) and Crystal Violet (CV) were purchased
from Merck Chemical Company and used as received. Anionic
Contact time effect
dyes Alizarin Yellow R (AY), Methyl Orange (MO) and Orange G
Sodium Salt (OG) were purchased from Alfa Aesar, Sigma- A mixture of aqueous initial CV dye concentrations of 500 mg
Aldrich and Amresco, respectively. All chemicals were used as L
1 and 100 mg of COPs (adsorbent) was shaken with an
received without any further purication. incubator shaker at 200 rpm for 5 h equilibrium time at room
temperature. Every 30 min, a sample was taken for UV-Vis
analysis.
Synthesis of covalent organic polymers (COPs)
Disulde-linked covalent organic polymers (COPs) were repro- Temperature
duced through catalyst-free oxidative coupling polymerization
according to our earlier method (Fig. 1).56 In a typical synthesis, The effect of the temperature for the removal of CV by using
trimethylolpropane tris(3-mercaptopropionate) (3SH) or pen- COPs was studied at different temperatures, namely, 25, 40, 55,
taerythritol tetrakis(3-mercaptopropionate) (4SH) was added 70 and 90  C. Again, the experiments were performed with
into DMSO, and the solution was heated at 80  C for 24 h under a solution containing an aqueous dye solution (concentration of
vigorous stirring. The reaction mixture was cooled down to 500 mg L
1) and 100 mg of COPs (adsorbent) using a incubator
room temperature. The precipitates were centrifuged and shaker at 200 rpm for 24 h equilibrium time.
soaked in THF for 12 h. Washing procedure was repeated four
times. Finally, a gel-like material was dried at 50  C for 2 h and Dye concentration
100  C for 5 h under vacuum to obtain COP-65 (by using 3SH) or The effect of the contact time for the removal of CV by using
COP-66 (by using 4SH). FTIR spectroscopy (VERTEX-70 Bruker, COPs was studied at different dye concentration such as, 100,
Germany) was used for the structural conrmations of each 200, 300, 400 and 500 mg L
1 for 5 h equilibrium time under the
synthesized COPs at room temperature (Fig. S1 in the ESI†). same conditions as the temperature variation study.
Solid-state cross polarization magic angle spinning (CP/MAS)
NMR spectra were recorded on a Bruker Avance III 400 WB Desorption and recyclability
NMR spectrometer (Fig. S2 in the ESI†).
To evaluate the possibility of regeneration of the dye-saturated
adsorbent, desorption experiments were carried out using
Adsorption studies tetrahydrofuran/water (50/50) solution in an ultrasonic gener-
All the adsorption experiments were carried out in 20 mL glass ator. 100 mg COPs (adsorbents) were added to 5 mL of dye
vials. Before adsorption experiments, calibration curves for solutions and the mixture was shaken on a rotary shaker at
each dye, CV, MB, RB, AY, MO and OG solutions (500 mg L
1) 200 rpm for 24 h. The initial dye concentration was 500 mg L
1.
were prepared by using Biochrom Libra S22 model UV-Vis At the end of the adsorption period, the dye-adsorbed COPs
spectrophotometer. The dye uptake study was performed adsorbents were soaked into 3 mL tetrahydrofuran for

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Paper RSC Advances

Fig. 1Schematic illustration for one pot, open air and easy synthesis of COPs by oxidative coupling of trimethylolpropane tris(3-mercapto-
propionate) and pentaerythritol tetrakis(3-mercaptopropionate) in DMSO.

desorption process. The suspensions were shaken on a rotary Methyl Orange (MO), Alizarin Yellow R (AY) and Orange G
shaker at 200 rpm for 24 h. Then the supernatant solutions were Sodium Salt (OG) as anionic dyes and Crystal Violet (CV),
analysed by using UV-Vis spectrometry. Methylene Blue (MB) and Rhodamine B (RB) as cationic (Fig. 2).
For all adsorption experiments, 100 mg of sorbent was treated
Characterisation with 3 mL aqueous solution (500 mg L
1) of the selected dye.
The micropollutant dye molecules have varying sizes as well.
In order to evaluate the porosity of COPs, N2 adsorption
We have recently shown that a rigid microporous polymer (COP-
isotherms were obtained with a Micromeritics Tristar II 3020
99) can do both size and charge dependent separation.2 Here,
accelerated surface area and porosimetry analyser at 77 K, aer
however, the network is made up of purely aliphatic monomers
the samples were degassed at 150  C for 5 h under vacuum prior
and prone to swelling with no initial porosity. We anticipate
to the measurements. The adsorption desorption isotherms were
a different mechanism, where guest molecules need to pene-
obtained to give BET (P/Po ¼ 0.01–0.25) and Langmuir (P/Po ¼
trate by expanding the network branches.
0.1–0.35) surface areas. The UV-Vis spectra from 190–900 nm were
Interestingly, both COPs showed a selective uptake towards
recorded using a Biochrom Libra S22 spectrometer using quartz
cationic dyes (Fig. 3). CV was the most captured dye molecule
cuvettes. Measurements of pH were obtained using an Orion
with capacities reaching up to 13.4 mg g
1 (with COP-65). RB
Research model SA250 digital pH meter. Zeta potential determi-
uptake reached 10.9 mg g
1 and MB has a maximum of 9.5 mg
nations of COP-65 and COP-66 were performed in aqueous 10
g
1 loading. However, the uptake of anionic dyes (AY, MO and
mM NaCl solutions by using Nano ZS, Malvern Instruments.
OG) by both COPs was negligible. The adsorption capacities of
anionic dyes were 0.425 mg g
1 (AY), 0.575 mg g
1 (MO) and
Results and discussion 0.325 mg g
1 (OG) by COP-65; and 0.337 mg g
1 (AY), 0.445 mg
g
1 (MO) and 0.267 mg g
1 (OG) by COP-66.
The hydrophobic, aprotic behaviour of COP-65 and COP-66 led
The high capture capacities for Crystal Violet (CV) allowed us
us to investigate adsorbent characteristics in removal of
to compare our results with that of others, surpassing all of the
contaminants with complex organic molecule nature.56 Due to
other low cost literature examples (Table 1).57–62 These values
the easy detection and the industrial relevance, we chose
suggest that the inexpensive COPs have great potential in
common textile dyes to be screened for removal activity. We,
selective cationic dye removal from aqueous solution. In that,
therefore, classied the target dyes in two groups: (1) anionic,
COPs behave uniquely and can serve as extractors from aqueous
and (2) cationic. Three dyes for each group were selected:

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Fig. 2 Chemical structures of the micro-pollutants; (a) anionic dyes: Alizarin Yellow (AY), Methyl Orange (MO) and Orange G (OG); (b) cationic
dyes: Methylene Blue (MB), Crystal Violet (CV) and Rhodamine B (RB).

Fig. 3(a) Adsorption capacities of COP-65 and COP-66 for six common anionic and cationic dyes, (b) digital pictures of anionic and cationic dye
uptake experiment (before and after 24 h) by COP-65.

25972 | RSC Adv., 2017, 7, 25969–25977 This journal is © The Royal Society of Chemistry 2017
Paper RSC Advances

Table 1 Comparison between the adsorption capacities of selective makes the surface of COPs less negatively charged due to
adsorbents towards Crystal Violet (CV) protonation.22 The pH of the aqueous solution is above 7, more
negatively charged surfaces of both COPs are formed due to the
Adsorption capacity
Adsorbents (mg g
1) References excess hydroxide ions (OH
). As the surfaces of COP-65 and
COP-66 become negatively charged at pH 8, there is signicant
Calotropis procera leaf 4.14 57 electrostatic attraction between the negatively charged surface
Jalshakti® polymer 12.9 58 of COPs and the cationic dye molecules, which leads to
Sugarcane dust 3.8 59
Neem sawdust 3.8 60
a maximum dye adsorption. However, above pH 8, the
Coir pith 2.56 61 hydroxide ions are in competition with the sorbent to combine
Sugarcane ber 10.44 62 with cationic species, which lead to lower dye adsorptions by
COPs 13.4 This work COPs due to the lack of substrate availability.22
In order to study the kinetics, we analysed the adsorption of
Crystal Violet (CV) with respect to contact time and temperature
medium. This, in contrast to well known all-purpose sorbents (Fig. 5). The rate of CV sorption was determined in varying time
like activated carbons, is quite different and only recently been intervals by mixing 500 mg L
1 of aqueous CV solution with
explored.2 100 mg of COP-65 or COP-66. Just aer the addition of COP-65
In order to understand why cationic dyes were taken up or COP-66, the dye adsorption started immediately. The
selectively, we measured surface charges of both COP struc- adsorption was increased sharply within 30 min and attained
tures. By using zeta potential readings, the surface charges of equilibrium aer 2 h (Fig. 5a). There is no signicant increase in
COP-65 and COP-66 were measured as
14.6 mV and
8.53 mV, removal of CV dye aer 2 h contact time.
respectively. Negative values generally correspond to the Effect of temperature on the adsorption of CV by COP-65 and
anionic species and electronegative atoms with lone pairs. We COP-66 at equilibrium was investigated at ve different
suspect that the network building by a single monomer with temperatures: 25, 40, 55, 70 and 90  C (Fig. 5b). We observed
thiol ends provides high thiol coverage of the surface, hence that the amount of adsorbed CV by COP-65 and COP-66
lone pairs. Deprotonation of the thiols also generate anionic increased from 12.4 to 14.6 mg g
1 and from 8.9 to 11.4 mg
sulphides and perhaps sulfonates from the oxidative coupling g
1, respectively, as the temperature was increased from 25 to
reaction. Ester groups on the branches of the network polymers 70  C. The enhanced adsorption at higher temperatures could
also contribute to the electron donating nature of the surface. be a result of an increase in the mobility of the dye molecules
The surface charges explain the favourable interaction, but (higher diffusion rate) and an easier swelling within COPs at
our ndings indicate that a swelling behaviour is mainly higher temperatures, which could enable the dye molecules to
responsible for the selective uptake. Despite the larger hydro- penetrate further inside.65 On the other hand, we found no
dynamic molecular size of the CV, it is adsorbed the most. This signicant change in the CV dye adsorption efficiency aer
leads to a conviction that uptake is not only due to surface 70  C, as it nears to the boiling point of water.
coverage of the dye molecules. Taking all these possibilities, we We also studied the dose of the dye molecules in adsorption
suggest a “gating approach” where surface charges form an capacities. Fig. 6a shows the adsorption capacity of COP-65
electrostatic barrier for rejection of similar charges. Then the against the contact time for varying initial concentrations
hydrophobic interior is swollen by the interaction of hydro- (100, 200, 300, 400 and 500 mg L
1) of the Crystal Violet (CV). A
carbon backbone of the dye molecules. A similar mechanism fast adsorption was observed for all concentrations during the
was observed when linear or branched hydrocarbons were rst 15 min due to the available surface area of the COPs for the
selectively separated on a metal–organic framework (MOF), adsorption of CV. Higher CV dye concentration led to an
Fe2(BDP)3.63 Most recently, using analogous concepts, Eddaoudi increase in the adsorption capacity of COP-65 due to the driving
and co-workers showed a very difficult separation of propylene force of the concentration gradient. The amounts of dye (mg
from propane by tailor-made MOF structure, KAUST-7.64 g
1) adsorbed on the COPs (Qe) increased from 4.516 to
Surface negative charge and the possibility of the deproto- 11.238 mg g
1 when the initial dye concentration changes from
nation prompted us to study in detail how the surface behaves. 100 to 500 mg L
1. Equilibrium of dye adsorption capacity was
We, therefore, carried out pH effect on the uptake capacities by attained for all dye concentrations aer 4 h.
both network polymers (Fig. 4). It is imperative that at lower pH Recyclability of the sorbents is ultimately important for any
values, a less negative surface is present, leading to a lower commercial feasibility. The COP-65 was tested in terms of its
uptake of cations. The experiments were conducted at various reusability for three consecutive cycles. 100 mg of COP-65 was
pH values (ranging from 2.0 to 10.0) with a 500 mg L
1 initial mixed into the 500 mg L
1 of CV solution. The desorption of
dye concentration and 100 mg of COP-65 and COP-66 (adsor- almost all adsorbed CV was achieved by treating with THF (a
bents) at room temperature for a day. The pH was adjusted by widely available industrial solvent) for 6 h (Fig. 6b). COP-65
adding either HCl or NaOH. The results indicate when the pH showed 94.4% adsorption of CV in the second cycle.56 There-
was changed from 2.0 to higher values up to 8.0, the amount of aer, the adsorbent showed slight decline in its performance,
cationic dyes adsorbed by COP-65 and COP-66 as shown in both in adsorption as well as desorption. The use of the same
Fig. 4a and b, respectively. At lower pH values, the hydrogen ion COP-65 in the third cycle showed 93.1% dye adsorption. We
(H+) ion concentration in the aqueous system is higher, which suspect that the remaining adsorbed dye molecules lead to

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Fig. 4 Adsorption performance of cationic dyes by (a) COP-65 (b) COP-66 in varying pH conditions.

Fig. 5 Effects of (a) contact time (inset shows the first hour) and (b) temperature on adsorption capacity of Crystal Violet (CV) on COP-65 and
COP-66.

Fig. 6(a) Effect of contact time on adsorption capacity of COP-65 with different concentrations of Crystal Violet (CV), (b) recycling experiment
of COP-65 for the adsorption and desorption of CV (500 mg L
1).

25974 | RSC Adv., 2017, 7, 25969–25977 This journal is © The Royal Society of Chemistry 2017
Paper RSC Advances

Fig. 7 The linear fittings for (a) Langmuir and (b) Freundlich adsorption isotherms for the sorption of Crystal Violet (CV) by COP-65.

decrease in both uptake and recovery of CV. Since the adsorp- indicates whether the nature of adsorption is favourable or not.
tion is purely physisorptive, mechanical or sonochemical A relatively high value of n (n > 1) indicates good adsorption
approaches could extract all trapped molecules. Our studies are intensity over the entire range of concentrations being
underway in that direction. studied.
The equilibrium adsorption isotherm plays an important role Linear plots of Ce/qe versus Ce and ln qe versus ln Ce are
in predictive modelling for design and optimization of adsorp- shown in Fig. 7. The values of qm and KL in the Langmuir
tion systems.66 In order to describe the relationship between the isotherm model and the values of KF and n in the Freundlich
amount of dye adsorbed and its equilibrium concentration in isotherm model are presented in Table 2. These results indicate
solution, we used two of the most commonly used models, that the CV dye in the aqueous solution is favourably adsorbed
Langmuir and Freundlich isotherms. Langmuir isotherm theory by the COP-65. The R2 value with respect to sorption of CV for
is based upon the assumption of monolayer adsorption on Langmuir isotherm model was noted to be 0.99657, which was
a homogeneous adsorbent.67,68 The linear form of the Langmuir 0.85131 for Freundlich isotherm model. It could be concluded
isotherm model can be written by using the equation below: from these observations that the adsorption of CV by using
Ce Ce 1 COP-65 was better dened by the Langmuir than Freundlich
¼ þ (1) isotherm model.
qe qm KL qm
where Ce (mg L
1) is equilibrium concentration of dye in solu-
tion, qm (mg g
1) is the maximum amount of dye per unit
weight of adsorbent, qe (mg g
1) is the amount of CV adsorbed
Conclusions
at equilibrium, KL (L mg
1) is the Langmuir equilibrium We have demonstrated selective cationic micropollutant (in this
adsorption constant related to the affinity of binding sites. The case textile dyes) removal from aqueous solutions by using
linear form of the Freundlich isotherm model was also used to covalent organic polymers (COPs) that were synthesized by
describe the equilibrium data by the following equation: catalyst-free oxidative coupling polymerization of tetravalent or
1 trivalent aliphatic thiols. COP-65 and COP-66 were obtained
ln qe ¼ ln KF þ ln Ce (2)
n from commercially available and inexpensive monomers, and
the resultant swellable insoluble networks exhibited unique
where KF (L mg
1) is Freundlich constant related to adsorption
uptake behaviour for three different cationic dyes. Interestingly,
intensity, 1/n is the order of adsorption constant which
only cationic dyes were taken in favourably by these sorbents.
Crystal Violet (CV) was captured the highest, despite its larger
hydrodynamic structure. As temperature, initial dye concen-
Table 2 The Langmuir and Freundlich isotherms model constants for trations or contact time increases, higher adsorption of CV was
the sorption of crystal violet from aqueous solution by COP-65
observed. The experimental data correlated well by the Lang-
Langmuir Freundlich muir adsorption isotherm compared to Freundlich ones. The
present study concludes that the disulde COPs could be
qm KL KF employed effectively as affordable adsorbents for the removal of
(mg g
1) (L mg
1) R2 (L mg
1) n R2
cationic micropollutants from aqueous media. In the future,
13.245 0.063 0.99657 2.287 2.886 0.85131 new and improved polymer networks will be evaluated for
a variety of potential applications and investigated with respect

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RSC Advances Paper

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