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z Materials Science inc. Nanomaterials & Polymers

Development of Mango Peel Derived Activated Carbon-

Nickel Nanocomposite as an Adsorbent towards Removal
of Heavy Metal and Organic Dye Removal from Aqueous
Solution
Saswata Bose,[a] Anirban Ghosh,[a] Arit Das,[b] and Mehabub Rahaman*[a]

In this study activated carbon has been prepared using waste RhB and Mn2 + was 88.7 % and 85.2 %, respectively, corroborat-
mango fruit peels as the precursor in a facile manner (MAC). In ing the reusability of the prepared adsorbent. The kinetics of
order to increase the efficiency and regenerability of activated the adsorption of RhB and Mn2 + ions on the surface of
carbon, nickel nanoparticles were impregnated. Morphological nanocomposite was found to follow the pseudo-second order
and crystalline structures of the prepared composite were model with a great degree of accuracy (R2 ∼ 0.99). The value of
investigated by field emission scanning electron microscopy the equilibrium parameter RL was found to be 0.015 and 0.003
(FESEM) and X-ray diffraction (XRD) analysis. MAC/Ni as an respectively for RhB and Mn2 + at 303 K which suggested that
adsorbent was found to remove 98 % and 93 % of Rhodamine B the Langmuir isotherm could be used to describe the favorable
(RhB) dye and manganese ions (Mn2 +) from their aqueous adsorption of the RhB dye and Mn2 + ions on the adsorbent
solutions. The regeneration study demonstrated that after the under the conditions used in the study.
completion of five adsorption cycles, the removal efficiency for

Manganese (Mn) removal from portable water sources has

Introduction
been a topic of much research in order to address issues
Over the span of the last three decades rapid development in concerning public health, proper functioning of distribution
various manufacturing sectors of textile, leather, paint, pharma- systems and aesthetic quality of water.[8] The main problem
ceutical, plastic, pesticide and leather industries have led to the associated with the presence of Mn2 + ions in water is that it
release of different heavy metal ions and synthetic dyes into can get oxidized to Mn3 + and Mn4 + ions which are insoluble in
the environment that constitutes a matter of serious concern water and imparts turbidity to the water.[9] Moreover, presence
as the discharge can be a likely source of carcinogens and of dissolved Mn2 + in water can lead to formation of scales
mutagens.[1,2] In order to curb the release of such harmful within pipes and cause various operational complications.[10]
substances and satisfy the stringent environmental regulations Generally the goal for water treatment plants is to reduce the
it must be ensured that the effluent stream containing the Mn concentrations below 0.02 mg/L which is an accepted
toxic contaminants are properly treated before their release threshold above which the aforementioned problems can
into the environment.[3] The proper treatment of both industrial occur.[11]
as well as household wastewater is an important issue in the Besides heavy metals like Mn, dyes are also a major
field of environmental science and technology that can play a contaminant present in industrial effluent streams that must be
vital role in water pollution control and subsequent removed for the safe discharge of such streams into water
purification.[4] Therefore, the appropriate treatment and poten- bodies. The problem associated with the treatment of dyes that
tial removal of hazardous materials from wastewater streams are used industries is that they neither degrade naturally or in
have attracted a lot of research interest.[5–7] presence of chemical agents. The existing physical or chemical
processes are expensive and hence cannot be used to treat
different dyes successfully. Also, the chemical and biological
treatments of many dyes are not feasible as they cannot
[a] Dr. S. Bose, A. Ghosh, Dr. M. Rahaman effectively treat solutions containing low concentrations of the
Department of Chemical Engineering
dyes. A common dye that is found in effluents is Rhodamine B
Jadavpur University
Kolkata-700032, India (RhB), which is widely used in painting, printing, textile and
E-mail: [email protected] leather industries despite being suspected of having toxic and
[b] A. Das carcinogenic effects on animal life.[12–14]
Department of Chemical Engineering
The different procedures and techniques that are used to
Virginia Polytechnic Institute and State University
Blacksburg, Virginia-24061, USA remove metal ions and organic dyes that have been used in
Supporting information for this article is available on the WWW under literature include photocatalysis, reverse osmosis, ion-resin
https://doi.org/10.1002/slct.202003606 exchange, electrochemical precipitation and adsorption.[15–19]

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Among all these methods, adsorption offers an inexpensive, XRD analysis of MAC and MAC/Ni
efficient and fast alternative to the other processes for the
removal of pollutants. Synthetic and natural polymers have Figure 1 shows the XRD spectra of MAC and MAC/Ni nano-
gained interest for their application as adsorbents but such composite powder. As shown in the figure, MAC exhibited
adsorbents suffer from the inherent drawbacks of high cost diffraction peaks at 2θ = 23.5° and 2θ = 43.8° which were
and poor reusability which has led to researchers to look into attributed to the diffraction of the (002) and (100/101) planes
low cost adsorbent materials.[20–22] In this regard, activated of amorphous MAC respectively. The appearance of these
carbon (AC) has been used as an adsorbent material for a peaks was indicative of the presence of graphitic crystallites in
variety of contaminants commonly found in wastewater due to the MAC powder. The broad nature of the peaks suggested
its excellent adsorption capacity. Moreover, researchers have that the lateral crystallite size (La) was relatively small.[33]
also investigated the adsorption performance of modified AC The MAC matrix contained a disordered structure which
adsorbents. Copper oxide nanoparticle loaded AC has been could be caused by a variety of different reasons such as,
found to be an effective adsorbent for the spontaneous localized stacking faults, fluctuating interlayer spacing and
removal of Acid blue 129 dye from liquid solutions.[23] strain within the layers.[34] The internal disordered structure led
Erythrosine dye has been treated using AC modified with zinc to the formation of a high specific surface area which is
sulfide and silver hydroxidenanoparticles where the kinetics of desirable for adsorption purposes. Since, the crystallinity was
the process was found to follow the pseudo-second order inversely related to the ordered structure of a sample, the
model with contribution from the inter particle diffusion specific surface area increased with the decrease in crystallinity
model.[24] Systematic design of experiments coupled with and therefore a decrease in the microcrystalline nature resulted
optimization by bee algorithm were carried out on the removal in a stronger activity of MAC. The XRD pattern of the MAC/Ni
of Cu2 + ions employing AC prepared from pomegranate wood exhibit two major peaks at 2θ = 44.5° and 2θ = 52.1° which
subsequently modified with thiourea based compounds.[25] A correspond to the face-centered cubic phase without any other
common synthetic dye used in food products have been additional peaks and the nanoparticles being crystalline single
successfully removed from wastewater by employing zinc phases.[35] The sizes of the crystallites corresponding to the two
hydroxide nanoparticle loaded AC but the process required major peaks were calculated using the classical Scherrer
ultrasonic irradiation to accelerate it.[26] equation (with a Scherrer constant of 0.9 and X-ray wavelength
Despite such promising works, the commercialization of of 0.15406 nm) and found to be 19.13 nm and 13.40 nm,
nanoparticle loaded AC on an industrial scale has been limited respectively. The Ni nanoparticles appeared to have dispersed
by two major factors, namely, dispersibility of AC in the in the MAC matrix with the favorable orientation along the
solution containing the contaminants and adsorbent regener- (111) and (200) plane with a0 = b0 = c0 = 0.3523 nm.[36] The peaks
ation costs.[27] Regeneration in solution phase results in the of the XRD pattern were consistent with JCPDS file no. 04-0850
generation of an effluent while that using thermal energy can for face-centered cubic structure of nickel.[37–39] It was also
result in loss of adsorbent which is economically not viable.[28] noticed that the peak at 23.5° corresponding to the (002) face
An alternative route to address the second issue is by of graphite disappeared for the MAC/Ni samples as the nickel
incorporating a magnetic material with AC to fabricate a nanoparticles dominated over the MAC as far as the crystalline
composite adsorbent that can be used for treating high contribution was concerned.
volumes of wastewater with decent performance.[29–31] Mag-
netic particles have been previously used in separation
processes and have been found to improve the adsorbent
performance due to enhanced electrostatic and π-π stacking
interactions between the adsorbate and adsorbent materials.[32]
In this work, MAC has been synthesized from dried mango
fruit peels, an abundant biomass waste, via a two-stage
physico-chemical activation process. In order to prepare an
adsorbent that can be easily recovered and reuse, the MAC was
combined with nickel nanoparticles which imparted magnetic
property to the composite besides improving the adsorption
ability. Morphological and crystalline structure of the prepared
composite (MAC/Ni) were investigated and its performance as
an adsorbent was evaluated by studying its adsorption
behavior (isotherms and kinetics) with respect to RhB and Mn2 +
contaminated water separately. The effect of pH and initial
concentration of the adsorbate was analyzed as well as the
desorption and regeneration properties in order to establish
the suitability MAC/Ni as a dual adsorbent for heavy metal ions
and organic dyes in field of water purification.
Results and Discussion Figure 1. XRD diffractogram of MAC and MAC/Ni.

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FESEM analysis of MAC and MAC/Ni exhibited a relatively clean surface compared to MAC/Ni but
the presence for pores was clearly observed.
Figures 2 (a,b) show the morphology of the MAC at different
magnifications while Figures 2 (c,d) illustrate the MAC/Ni
Effect of pH
morphology at different magnifications as observed using the
field emission scanning electron microscope (FESEM). The The pH of the wastewater solution has been attributed to be
surface morphology of the MAC/Ni as adsorbent exhibited non- one of the most important parameters that can have a
uniformity with numerous discernible cavities which may have pronounced effect on the adsorption process.
contributed to the increased surface area required for the dye The reason behind pH being such a major factor is due to
molecules and metal ions to interact with the adsorbent. The the effect it has on the surface charge of the adsorbent,
micrograph also showed the rough and porous structure of the dissociation of the adsorbate on the active sites and the extent
adsorbents. The incorporation of the nickel nanoparticles of electrostatic interaction between the adsorbate and adsorb-
tailored the morphology to an appreciable extent as evidenced ent. Figure 3 shows the effect of pH on the removal efficiency
by the cracking of the surface and wear of the surface particles. of the prepared adsorbent with respect to RhB and Mn2 +. As is
Moreover, it was found that the surface pores were of varying evident from the data shown in the figure, the adsorption of
sizes and they were held responsible for the efficient both the dye and metal ion was found to be dependent on the
adsorption performance. The pores were large enough to allow pH of the solution. The equilibrium removal efficiency was
the dye molecules or metal ions to penetrate and get adsorbed found to increase for RhB and Mn2 + in the range of 1–3 and 1–
on the surface after interacting with the functionalities present 5 respectively. The removal efficiency decreased appreciably as
at those sites. On the other hand, FESEM image of MAC the pH of the solution became progressively more and more
basic. The maximum removal efficiency was observed at pH = 3
for RhB and pH = 5 for Mn2 +. Similar trend in the pH depend-
ence was found for the removal of RhB using pine needles.[40]
At lower pH, RhB exist in cationic monomer form but at pH
higher than 4 it exists as a zwitterion. So despite RhB being
positively charged at pH = 3, it was found to be the optimum
condition for RhB removal. The reason for such behavior may
be due to the easy diffusion of the monomeric dye molecules
into the active sites of the adsorbent compared to the bulky
zwitterionic dimer form. Therefore, all the batch and kinetic
experiments in the following sections for RhB removal were
conducted at pH = 3. For the case of the Mn2 + ions, the -COO
ligands present on the surface of the adsorbent may attract the
metal cations and bind to form an electrostatic bond. At initial
low values of pH, the removal efficiency did not change
appreciably since the excess H + ions in the acidic solution
prevented Mn2 + ions from binding to the adsorbent. The
maximum removal efficiency was observed at pH = 5. However,
at pH higher than 5, the active sites undergo deprotonation
which results in the accumulation of a negative charge density
Figure 2. FESEM images of (a, b) MAC and (c, d) MAC/Ni.
on the surface of the adsorbent. The negatively charge density
attracts the Mn2 + ions and facilitates their binding with the
adsorbent. On the other hand, the carboxylate ions from the
dye being similarly charged experiences repulsion while
approaching the negatively charged adsorbent under such
conditions (pH > 5). Hence, a drastic drop in dye removal by
the adsorbent is noticeable when the pH of the solution is
higher than 5. The batch and kinetic experiments for Mn2 +
removal was performed at pH = 5 since the percentage removal
was highest at that condition.

Batch equilibrium experiments

The batch equilibrium data was used to generate the removal
efficiencies of both RhB (Figure 4a) and Mn2 + (Figure 4b). It was
Figure 3. Variation of Percentage Removal as a function of pH for (a) observed that during the adsorption of both Mn2 + and RhB by
Rhodamine-B dye solution; (b) Manganese (Mn2 +) metal ion. MAC/Ni sample there were no discrepancies in the adsorption

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Figure 4. Variation of Percentage Removal vs. Time using MAC/Ni for (a) Rhodamine-B dye solution; (b) Manganese (Mn2 +) metal ion.

process. While performing similar experiments using MAC It has been observed that MAC was not stable enough at
instead of MAC/Ni, desorption was observed to accompany higher percentage removal of the RhB as well as the Mn2 +.
along with the process of adsorption (Figures 5a and b). After However effect of Ni2 + metal nanoparticle enhanced the
attaining more than 90 % removal in both cases the stability of effectiveness of MAC as adsorbent of dye and the metal ions.
MAC as an adsorbent was slightly compromised. In case of the But, MAC by itself could adsorb a significant amount of dye
equilibrium study for RhB, MAC was seen to continuously and Mn2 + metal ion but it was not stable at near saturation
adsorb and desorb certain amount of dye once more than 98 % adsorption region.
removal was attained (Figure 5a). On the other hand, in case of
Mn2 + removal equilibrium was attained at a maximum removal
Kinetics of sorption experiments
efficiency of 92.7 % and then a trend of desorption was noted
where the removal efficiency dropped down to 90.5 % over the The time required for the achievement of equilibrium from the
course of the 24-hour experiment (Figure 5b). point of addition of the adsorbent is a key factor in facilitating
its application in wastewater treatment from the economical

Figure 5. Variation of Percentage Removal as a function of Time over 24 hours using MAC for (a) Rhodamine-B dye solution; (b) Manganese (Mn2 +) metal ion

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point of view. The mechanism of the adsorption process was describe the kinetics of the fixation reaction of adsorbate on
analyzed using three different kinetic models. First, the the adsorbent:[42–44]
adsorption kinetics was examined using the pseudo first order
model which was proposed by Lagergren which is expressed as t 1 t
¼ þ
follows:[41] qt k2 q2e qe

lnðqe qt Þ ¼ lnðqe Þ k1 * t where, k2 (g mg 1 h 1) is the second order adsorption rate

constant. This model is valid if the plot of t/qt vs. time (t) yields
where, qe and qt are the amounts of metal ion or dye adsorbed a straight line. The model constants (qe and k2) were evaluated
(mg g 1) at equilibrium and at time t (h) respectively, and k1 from the slope and intercept of the plot respectively. The linear
(h 1) is the first order adsorption rate constant. A straight line plot of t/qt versus t obtained at 303 K, as shown in Figures 7 (a,
of ln(qe-qt) vs. time (t) corroborates the validity of the pseudo b) for RhB and Mn2 + respectively, exhibited excellent R2 values
first order kinetic model. The model constants (qe and k1) were for both the dye and metal ion indicative of good agreement
evaluated from the intercept and slope of the plots of pseudo between the experimental and model predicted results. Thus
first order plots of RhB and Mn2 +, respectively (Figures 6a and the pseudo-second order model can be used to describe the
b). However, for the kinetics of the adsorption process under adsorption of RhB and Mn2 + ions on the surface of MAC/Ni
study, the pseudo-first order model did not provide a with a great degree of accuracy.
satisfactory fit to the kinetic data obtained. The mechanism of diffusion during the adsorption process
So to explain the kinetics of the adsorption process in the was studied using the intraparticle diffusion model which is
present study we used the pseudo-second-order equation to expressed as follows:[45]

Figure 6. Pseudo First Order kinetic model Plots for (a) Rhodamine-B dye solution; (b) Manganese (Mn2 +) metal ion.

Figure 7. Pseudo Second Order kinetic model Plots for (a) Rhodamine-B dye solution; (b) Manganese (Mn2 +) metal ion.

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qt ¼ Kp t0:5 it must be kept in mind that the model assumes only a fixed
number of energetically invariant active sites with no move-
ment of the adsorbate molecules across the adsorption plane.
where, Kp (mg g 1 h 0.5) is the intraparticle diffusion rate The Langmuir isotherm in its linear form is shown below:
constant which can be estimated from the slope of qt vs. t0.5
plot. This model basically has three different regimes, namely, Ce 1 C
¼ þ e
the external surface adsorption regime, intraparticle diffusion qe Q0 b Q0
limited regime and final equilibrium regime where the intra-
particle diffusion becomes less prominent due to the vanish- where, Ce is the equilibrium concentration of the adsorbate, qe
ingly low concentrations of the adsorbate left in the solution.[46] is the mass of adsorbate adsorbed per unit mass of adsorbent,
From the plot for the intraparticle diffusion model for the Q0 and b are Langmuir constants which are dependent on the
present case we observe that it does not pass through the adsorption capacity and rate respectively. Figures 9a and 9b
origin (Figures 8a and b for RhB and Mn2 + respectively) which shows the Langmuir model for the adsorption of RhB and
could be attributed to the variation in the rate of mass transfer Mn2 +.
at the initial and final stages of adsorption due to a decrease in Table 2 shows the applicability of these isotherm models
the concentration gradient existing between the adsorbent for the present case involving the MAC/Niadsorbent and the
surface and solution which is the driving force for the mass values of the constants obtained by fitting the data. The main
transfer. Table 1 shows the applicability of these kinetic models constant obtained from the Langmuir analysis has been
for the present case involving the MAC/Ni adsorbent and the expressed as a equilibrium parameter (RL) which is defined as:
values of the constants obtained by fitting the kinetic data
obtained during the adsorption experiments. 1
RL ¼
1 þ b*C0

Adsorption isotherms
where b is the Langmuir constant and C0 is the highest dye or
The equilibrium adsorption data were fitted using a couple of metal ion concentration (mg/l). RL values are indicative of the
different isotherm models to get an insight into the mechanism type of adsorption that is taking place, namely favorable (0 <
of adsorption. Firstly, the traditional Langmuir isotherm which RL < 1), unfavorable (RL > 1), linear (RL = 1) or irreversible (RL = 0).
assumes a simple monolayer adsorption was used.[47] Moreover, For the given case the value of RL was found to be 0.015 and

Figure 8. Intra Particle Diffusion model Plots for (a) Rhodamine-B dye solution; (b) Manganese (Mn2 +) metal ion.

Table 1. Validity of Kinetic Models and Parameter Estimation for the MAC/Ni Adsorbent.

Component Concentration Model R2 Parameters Error (%)

Rhodamine B (RhB) 10 μM Pseudo First Order 0.81698 qe = 0.7409 mg/g 84.40

k1 = 0.2010 h 1
Pseudo Second Order 0.99996 qe = 4.7897 mg/g 0.8364
k2 = 0.92526 g/mg h
Manganese (Mn + 2) 250 mg/L Pseudo First Order 0.91394 qe = 460.3732 mg/g 0.2032
k1 = 0.4439 h 1
Pseudo Second Order 0.99583 qe = 487.8048 mg/g 5.7433
k2 = 0.002011 g/mg h

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Figure 9. Langmuir Isotherm Plots for (a) Rhodamine-B dye solution; (b) Manganese (Mn2 +) metal ion.

Table 2. Validity of Kinetic Models and Parameter Estimation for the MAC/
Ni Adsorbent. the surface coverage. The linearized form of the Freundlich
2
model is shown below:
Component Isotherm Model Constants R
Model
1
Rhodamine B Langmuir Q0 = 15.7233 mg/g 0.9905 logðqe Þ ¼ logðKF Þ þ * logðCe Þ
n
(RhB) b = 6.766 l/mg
RL = 0.01516
Freundlich KF = 12.9583 mg/g (l/ 0.94657 where, KF is the adsorption coefficient that is indicative of the
mg)1/n amount of adsorbate adsorbed on the surface of the adsorbent
1/n = 0.38771
for a unit equilibrium concentration and n is the Freundlich
Manganese Langmuir Q0 = 403.2258 mg/g 0.94616
(Mn + 2) b = 1.24 l/mg constant which determines the favorability of the adsorption
RL = 0.003215 process. Figures 10a and 10b shows the Freundlich plot for RhB
Freundlich KF = 135.1263 mg/g (l/ 0.97235 and Mn2 + adsorption. The value of 1/n between 0 and 1
mg)1/n
provides a quantitative measure of the adsorption intensity
1/n = 0.33975
which transitions to a more non-uniform distribution as the
value approaches zero.[48] On the other hand, a value of less
than 1 for 1/n suggests that a normal Langmuir isotherm can
0.003 respectively for RhB and Mn2 + at 303 K which suggested explain the adsorption process without loss of generality while
that the Langmuir isotherm can be used to validate the a value greater than 1 is a characteristic of cooperative
favorable adsorption of the dye and metal ions on MAC/Ni adsorption.[49] In the current study, 1/n values are 0.38771 and
under the conditions used in the study. 0.33975 for RhB and Mn2 +, respectively. Table 3 compares the
Another isotherm model that was used to fit the data was adsorption capacity of the prepared MAC/Ni adsorbent with
the Freundlich isotherm that assumes heterogeneous distribu- other adsorbents reported in literature for the removal of heavy
tion of surface energy of the active sites which is dependent on metals and dyes.

Figure 10. Freundlich Isotherm for (a) Rhodamine-B dye solution; (b) Manganese (Mn + 2) metal ion.

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Table 3. Comparison of adsorption capacity of different adsorbents with efficiency to its original value (98.3 % for the dye and 93.6 % for
the one prepared in this study. the Mn2 +). The acid washing of the adsorbent did not adversely
Adsorbent Contaminants Amount adsorbed
affect the stability of Ni particles since at ambient temperatures
(mg g 1) Ni is only sparingly soluble in dilute HCl.[60,61] Moreover, the
magnetic properties of the adsorbent were retained post-
AC from coir pith[50] Congo red 6.72
AC from sludge[51] Acid brown 20.5
washing with HCl since the reused adsorbent remained
283 responsive to a bar magnet even at the end of five washing
AC from almond shell[52] Methylene 1.33 cycles. This finding was promising since it indicated that the
blue prepared adsorbent could be easily regenerated and thus can
Commercial AC[53] Acid brown 7.83
425
be used multiple times. Finally, since the separation of the
AC from sugarcane bagasse[54] Acid orange 5.78 adsorbent from the treated wastewater solution using an
10 external magnetic field was simple, it was expected that such
Granular AC[55] Manganese 7.63 magnetic adsorbents could have potential industrial applica-
AC immobilized with tannic Manganese 1.73
acid[56]
tions by avoiding secondary pollution that is very common in
AC from Jujube seeds[57] Manganese 172 existing wastewater treatment procedures.
AC from bean pods[58] Manganese 23.4
Granular AC[59] Manganese 2.54
MAC/Ni Rhodamine B 15.72 Conclusion
(Present study)
MAC/Ni(Present study) Manganese 403.22 From the above study it can be concluded that the prepared
AC from biodegradable waste (mango fruit peels) can be used
to adsorb both heavy metals and organic dyes. The impregna-
tion of MAC with Ni nanoparticles significantly improved the
adsorption kinetics and adsorption capacity during remediation
Desorption and regeneration
of Mn2 + and RhB from aqueous solutions under similar
The regeneration efficiency of the adsorbent with respect to loadings. The adsorption of RhB and Mn2 + was found to be
RhB dye and Mn2 + ions has been shown in Figure 11. The most efficient at pH ∼ 3 and pH ∼ 5 respectively. The pseudo-
values reported in the figure were an average of three runs. It second order model could be employed to describe the
was observed that there was no significant change in the adsorption of RhB and Mn2 + ions on the surface of MAC/Ni
removal efficiency of RhB and Mn2 + after the first sorption with a great degree of accuracy. Langmuir isotherm was found
cycle. However, with the progression in the number of cycles to be the best fit for the adsorption of both dye and Mn2 + ions.
the efficacy of the contaminant removal decreased which was The adsorbent could be easily separated from the treated
most probably due to the pore blockage over time. It was wastewater solution using an external magnetic field and
found that after the completion of five cycles, the removal regenerated upon which the removal efficiency was restored
efficiency for RhB and Mn2 + was 88.7 % and 85.2 % respectively. close to the initial value thereby allowing multiple usage. The
The adsorbent was removed from the aqueous solution using a overall results suggest that MAC/Ni has the potential of being
magnet at this point; filtered and subjected to a regeneration used as a low-cost adsorbent at an industrial scale for treating
wash using 1 molL 1 HCl solution which restored the removal effluent streams that are contaminated with both organic dyes
and heavy metals ions while avoiding secondary pollution
because of its reusability characteristics.

Supporting Information Summary

Supporting information includes the table of content and the
experimental section. Experimental section consists of chem-
icals used, details of the preparative methods to produce
activated carbon from mango peels (MAC), preparation of
activated carbon-nickel nanocomposite, XRD, SEM character-
ization techniques, batch equilibrium and kinetic studies, and
regeneration studies.

Acknowledgements
The authors would like to acknowledge the start-up grant under
the “Faculty Recharge Programme” to Dr. Saswata Bose to carry
out the present work by the University Grants Commission, New
Figure 11. Regeneration efficiency of the adsorbent with respect to Rhod- Delhi, Government of India.
amine-B dye solution and Manganese (Mn + 2) metal ion.

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[29] A. L. Cazetta, O. Pezoti, K. C. Bedin, T. L. Silva, A. Paesano Junior, T. Asefa,

Conflict of Interest V. C. Almeida, ACS Sustainable Chem. Eng. 2016, 4, 1058–1068.
[30] T. A. Saleh, M. Tuzen, A. Sari, J. Environ. Chem. Eng. 2017, 5, 2853–2860.
The authors declare no conflict of interest. [31] X. Song, C. Wang, M. Liu, M. Zhang, Water Sci. Technol. 2018, 77, 1891–
1898.
[32] L. Ai, C. Zhang, F. Liao, Y. Wang, M. Li, L. Meng, J. Jiang, J. Hazard. Mater.
Keywords: activated carbon · adsorption · kinetics · nickel 2011, 198, 282–290.
nanocomposite · waste mango peel [33] B. Sakintuna, O. Çuhadar, Y. Yürüm, Energy Fuels 2006, 20, 1269–1274.
[34] V. Suresh Babu, M. S. Seehra, Carbon N. Y. 1996, 34, 1259–1265.
[1] A. Ergene, K. Ada, S. Tan, H. Katircioǧlu, Desalination 2009, 249, 1308– [35] R. A. Landa, P. Soledad Antonel, M. M. Ruiz, O. E. Perez, A. Butera, G.
1314. Jorge, C. L. P. Oliveira, R. M. Negri, J. Appl. Phys. 2013, 114, 213912.
[2] I. Kiran, S. Ilhan, N. Caner, C. F. Iscen, Z. Yildiz, Desalination 2009, 249, [36] S. Nandy, S. Mallick, P. K. Ghosh, G. C. Das, S. Mukherjee, M. K. Mitra, K. K.
273–278. Chattopadhyay, J. Alloys Compd. 2008, 453, 1–6.
[3] C. Santhosh, V. Velmurugan, G. Jacob, S. K. Jeong, A. N. Grace, A. [37] L. N. Tsai, G. R. Shen, Y. T. Cheng, W. Hsu, J. Microelectromech 2006, 15,
Bhatnagar, Chem. Eng. J. 2016, 306, 1116–1137. 149–158.
[4] V. Rocher, J. M. Siaugue, V. Cabuil, A. Bee, Water Res. 2008, 42, 1290– [38] J. Li, P. Li, J. Li, Z. Tian, F. Yu, Catalysts 2019, 9, 506.
1298. [39] W. Ni, B. Wang, J. Cheng, X. Li, Q. Guan, G. Gu, L. Huang, Nanoscale
[5] M. R. Awual, T. Yaita, S. Suzuki, H. Shiwaku, J. Hazard. Mater. 2015, 291, 2014, 6, 2618.
111–119. [40] M. R. R. Kooh, M. K. Dahri, L. B. L. Lim, Cogent Environ. Sci. 2016, 2, DOI
[6] Z. Hasan, S. H. Jhung, J. Hazard. Mater. 2015, 283, 329–339. 10.1080/23311843.2016.1140553.
[7] N. A. Khan, B. K. Jung, Z. Hasan, S. H. Jhung, J. Hazard. Mater. 2015, 282, [41] LAGERGREN, S., Zeitschrift für Chemie und Ind. der Kolloide 1907, 2, 15–
194–200. 15.
[8] J. E. Tobiason, A. Bazilio, J. Goodwill, X. Mai, C. Nguyen, Curr. Pollut. [42] G. Blanchard, M. Maunaye, G. Martin, Water Res. 1984, 18, 1501–1507.
Reports 2016, 2, 168–177. [43] T. Gosset, J. L. Trancart, D. R. Thévenot, Water Res. 1986, 20, 21–26.
[9] M. Keiluweit, P. Nico, M. E. Harmon, J. Mao, J. Pett-Ridge, M. Kleber, Proc. [44] Y. S. Ho, G. McKay, Process Biochem. 1999, 34, 451–465.
Natl. Acad. Sci. USA 2015, 112, E5253–E5260. [45] F. C. Wu, R. L. Tseng, R. S. Juang, Chem. Eng. J. 2009, 153, 1–8.
[10] A. A. Islam, J. E. Goodwill, R. Bouchard, J. E. Tobiason, W. R. Knocke, J. / [46] F. C. Wu, R. L. Tseng, R. S. Juang, J. Colloid Interface Sci. 2005, 283, 49–56.
Am. Water Work. Assoc. 2010, 102, 71–83. [47] T. W. Weber, R. K. Chakravorti, AIChE J. 1974, 28, 228–238.
[11] R. J. Casale, M. W. LeChevallier, F. W. Pontius, 2002. [48] F. Haghseresht, G. Q. Lu, Energy and Fuels 1998, 12, 1100–1107.
[12] S. K. Das, J. Bhowal, A. R. Das, A. K. Guha, Langmuir 2006, 22, 7265–7272. [49] K. Fytianos, E. Voudrias, E. Kokkalis, Chemosphere 2000, 40, 3–6.
[13] C. Namasivayam, R. Radhika, S. Suba, Waste Manage. 2001, 21, 381–387. [50] C. Namasivayam, D. Kavitha, Dyes Pigm. 2002, 54, 47–58.
[14] J. Rochat, P. Demenge, J. C. Rerat, Toxicol. Eur. Res. 1978, 1, 23–26. [51] M. J. Martin, A. Artola, M. D. Balaguer, M. Rigola, Chem. Eng. J. 2003, 94,
[15] N. Ezzatahmadi, G. A. Ayoko, G. J. Millar, R. Speight, C. Yan, J. Li, S. Li, J. 231–239.
Zhu, Y. Xi, Chem. Eng. J. 2017, 336–350. [52] A. Aygün, S. Yenisoy-Karakaş, I. Duman, Microporous Mesoporous Mater.
[16] J. Gómez-Pastora, E. Bringas, I. Ortiz, Chem. Eng. J. 2014, 187–204. 2003, 66, 189–195.
[17] L. Ren, H. Lu, L. He, Y. Zhang, Chem. Eng. J. 2014, 111–124. [53] V. Gómez, M. S. Larrechi, M. P. Callao, Chemosphere 2007, 69, 1151–1158.
[18] C. Santhosh, V. Velmurugan, G. Jacob, S. K. Jeong, A. N. Grace, A. [54] W. T. Tsai, C. Y. Chang, M. C. Lin, S. F. Chien, H. F. Sun, M. F. Hsieh,
Bhatnagar, Chem. Eng. J. 2016, 1116–1137. Chemosphere 2001, 45, 51–58.
[19] S. Wang, H. Sun, H. M. Ang, M. O. Tadé, Chem. Eng. J. 2013, 336–347. [55] M. E. Goher, A. M. Hassan, I. A. Abdel-Moniem, A. H. Fahmy, M. H. Abdo,
[20] R. S. Blackburn, Environ. Sci. Technol. 2004, pp. 4905–4909. S. M. El-sayed, Egypt. J. Aquat. Res. 2015, 41, 155–164.
[21] P. Francesca, M. Sara, T. Luigi, Water Res. 2008, 42, 2953–2962. [56] A. Üçer, A. Uyanik, Ş. F. Aygün, Sep. Purif. Technol. 2006, 47, 113–118.
[22] M. T. Uddin, M. A. Islam, S. Mahmud, M. Rukanuzzaman, J. Hazard. Mater. [57] A. Omri, M. Benzina, Alexandria Eng. J. 2012, 51, 343–350.
2009, 164, 53–60. [58] T. Budinova, D. Savova, B. Tsyntsarski, C. O. Ania, B. Cabal, J. B. Parra, N.
[23] F. Nekouei, S. Nekouei, I. Tyagi, V. K. Gupta, J. Mol. Liq. 2015, 201, 124– Petrov, Appl. Surf. Sci. 2009, 255, 4650–4657.
133. [59] A. bin Jusoh, W. H. Cheng, W. M. Low, A. Nora’aini, M. J. Mega-
[24] M. Ghaedi, Z. Rozkhoosh, A. Asfaram, B. Mirtamizdoust, Z. Mahmoudi, t Mohd Noor, Desalination 2005, 182, 347–353.
A. A. Bazrafshan, Spectrochim. Acta Part A 2015, 138, 176–186. [60] X. Ling, F. Du, Y. Zhang, Y. Shen, T. Li, A. Alsaedi, T. Hayat, Y. Zhou, Z.
[25] A. M. Ghaedi, M. Ghaedi, A. Vafaei, N. Iravani, M. Keshavarz, M. Rad, I. Zou, RSC Adv. 2019, 9, 33558–33562.
Tyagi, S. Agarwal, V. K. Gupta, J. Mol. Liq. 2015, 206, 195–206. [61] K. Shang, Y. Z. Yang, J. X. Guo, W. J. Lu, F. Liu, W. Wang, Asian J. Chem.
[26] M. Roosta, M. Ghaedi, R. Sahraei, M. K. Purkait, Mater. Sci. Eng. C 2015, 2012, 24, 546–550.
52, 82–89.
[27] X. Luo, L. Zhang, J. Hazard. Mater. 2009, 171, 340–347.
[28] P. Waranusantigul, P. Pokethitiyook, M. Kruatrachue, E. S. Upatham, Submitted: September 12, 2020
Environ. Pollut. 2003, 125, 385–392. Accepted: November 16, 2020

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