Hindawi

Journal of Chemistry
Volume 2024, Article ID 4008315, 19 pages
https://doi.org/10.1155/2024/4008315

Research Article
Sorption Mechanisms and Enhancement of Selected
Organochlorine Pollutants in Water on Zeolites

Timothy Manda ,1 Solomon Omwoma ,1 Godfrey Okumu Barasa ,1

Anthony M. Pembere ,1 Douglas Sifuna ,1 Livingstone Ochilo ,1 Silas Lagat ,1
Emily Ngeno ,2 Patrick Ssebugere ,3,4,5 Christine Betty Nagawa ,6
and Christine Kyarimpa 7
1
Department of Physical Sciences, Jaramogi Oginga Odinga University of Science and Technology, Bondo (Main) Campus,
P.O. Box 210-40601, Bondo, Kenya
2
Department of Physical Sciences, Kaimosi Friends University, P.O. Box 385–50309, Kaimosi, Kenya
3
Department of Chemistry, Makerere University, P.O. Box 7062, Kampala, Uganda
4
Department of Cell Toxicology, Helmholtz Centre for Environmental Research−UFZ, D-04318 Leipzig, Germany
5
Department of Analytical Environmental Chemistry, Helmholtz Centre for Environmental Research−UFZ,
D-04318 Leipzig, Germany
6
Department of Forestry, Bio-Diversity and Tourism, Makerere University, P.O. Box 7062, Kampala, Uganda
7
Department of Chemistry, Kyambogo University, P.O. Box 1, Kyambogo, Uganda

Correspondence should be addressed to Solomon Omwoma; [email protected]

Received 14 April 2023; Revised 29 November 2023; Accepted 23 December 2023; Published 8 January 2024

Academic Editor: Ajaya Kumar Singh

Copyright © 2024 Timothy Manda et al. Tis is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.
Tis study investigates the adsorption capacities of selected organochlorines on zeolites, focusing on hexachlorobenzene
(HCB), hexachlorotetradecane (HCTD), hexachlorodecane (HCD), hexachlorocyclohexane (HCH), heptachlorodecane
(HPCD), octachlorodecane (OCD), dichlorodiphenyltrichloroethane (DDT), and octachlorotetradecane (OCTD). Te
structures of the organochlorines were optimized and their Frontier molecular orbitals were calculated. Te analysis of
HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energies provided insights
into the molecules’ electron-donating and -accepting capabilities. Te present research identifed the universal force feld as
suitable for the investigation and used it to evaluate the adsorption capacities of the pollutants on various zeolites. It was
found that CLO (a cubic microporous gallophosphate) demonstrated the highest adsorption capacity for HCB among 245
zeolites, with a loading capacity of 65.84 wt%. In terms of molecules adsorbed per cell, CLO remained the highest with 120
molecules per cell for HCB, 113 molecules per cell for HCH, 43 molecules per cell for DDT, 21 molecules per cell for HCTD,
19 molecules per cell for OCTD, 47 molecules per cell for HCD, 30 molecules per cell for HPCD, and 22 molecules per cell for
OCD. Te analysis revealed correlations between the structural parameters of zeolites (mass, density, HVF, APV, VSA, GSA,
DPS, and Di) and their adsorption capacities. Te investigation delved into cluster models to understand the interaction of
organochlorines with the zeolite framework. Te study explored the impact of doping CLO zeolite with diferent atoms (Al,
Si, and Na) on adsorption capacity. Te results showed that doping with aluminum improved both loading capacity and
adsorption energy and dissociate the chlorinated compounds during adsorption. Quantum chemical calculations show that
hydrogen-based bonding of the organochlorides on the CLO is thermodynamically favorable compared to dissociative
adsorption. In addition, oxygen atoms in the zeolites provide active adsorption sites. In the present work, laboratory
adsorption experiments were performed, treating zeolites with heat at 400°C. Surprisingly, untreated zeolites outperformed
treated ones, adsorbing up to 91% of HCB, while treated zeolites reached saturation after the third run. Te study attributed
the better performance of untreated zeolites to the presence of interstitial water and hydrogen atoms, which are critical for
electrostatic interactions with organic compounds. In general, this research provides a comprehensive analysis of the
adsorption capacities of organochlorines on zeolites, combining computational simulations and laboratory experiments.
2 Journal of Chemistry

Tis work’s distinctive quality is its methodology that combines molecular simulations, experimental verifcation, doping, and
interstitial water efects. Te fndings emphasize the importance of zeolite (a high-porosity nanostructured material) structure,
composition, and treatment methods in determining their efectiveness as adsorbents for environmental pollutants.

1. Introduction in various industrial and agricultural activities, are challenging

to remediate due to their stability. Te study addresses this
Several studies have shown that zeolites are good adsorbents of environmental concern by investigating their adsorption on
various contaminants [1]. Tese crystalline solids are ecologi- zeolite surfaces, aiming to contribute valuable insights for
cally friendly, but their framework composition has a great efective pollutant removal strategies. Te choice is pragmatic,
efect on the quantity of their micropores and other physico- aligning with the study’s goal of addressing real-world chal-
chemical characteristics [2, 3]. By adjusting the SiO2/Al2O3 ratio lenges and ofering practical solutions.
(SAR), these materials’ hydrophilic/hydrophobic properties can Te historical background of the study on zeolite ad-
be adjusted [4, 5], while high porosity and vast surface areas are sorption of organochloride pollutants traces back to the 18th
imparted to them by their 3D framework, which creates century, where the unique properties of zeolites frst cap-
nanometer-sized channels and cages [6-7]. On the other hand, tivated scientists. Troughout the mid-20th century, sys-
the adsorption selectivity towards host molecules is signifcantly tematic research into zeolite properties, including
infuenced by the interior pore structure’s shape. Tese factors framework composition and surface chemistry, laid the
have led to the usage of zeolites as adsorbent media for par- foundation for their application in adsorption processes. Te
ticular chemical classes, including hydrocarbons [8, 9, 10], development of molecular mechanical techniques and sta-
halocarbons [11, 12], and pharmaceuticals [13, 14, 15]. tistical physics models in the latter half of the 20th century
Te selection of zeolites as the primary focus in this study enabled a more precise understanding of zeolite-guest in-
stems from their exceptional attributes that make them highly teractions at the atomic level. Te 21st century saw a growing
suitable for the investigation of organochlorine compounds. environmental awareness, prompting a search for sustain-
Zeolites possess a remarkable adsorption capacity owing to able solutions to water pollution. Zeolites, with their eco-
their extensive surface area and porous structure, providing an friendly nature and versatile adsorption capabilities, gained
ideal environment for capturing and retaining pollutants [16]. prominence for environmental remediation. Recent ad-
Te diverse structural frameworks among zeolite types ofer vancements, such as the discovery of stable H-bonded ad-
a nuanced exploration into how these variations infuence the ducts during drug adsorption on zeolites, fueled further
adsorption performance of organochlorines. Moreover, the exploration of zeolite-based solutions for removing organic
distinctive surface chemistries of zeolites, characterized by contaminants. Te ongoing research outlined in the study
specifc functional groups and charge distribution, play a piv- represents a continuation of historical developments. It aims
otal role in understanding the nuanced interactions with to deepen our understanding of zeolite-guest interactions
targeted pollutants. Te molecular sieving efect, facilitated by and expand zeolite applications by exploring modifcations
the porous nature of zeolites, ensures selective adsorption based to their surfaces through functionalization and the in-
on the size and shape of molecules. In addition, the cation corporation of additional materials. Te study refects the
exchange capacity intrinsic to zeolites is a crucial aspect that enduring quest for innovative and sustainable technologies
enhances their efectiveness in capturing and immobilizing to address environmental challenges.
pollutants. By delving into the impact of surface area, pore size Organic molecules adsorption on zeolites adsorbents can
distribution, and thermal stability—properties inherent to involve both nonspecifc (ionic) and specifc interactions
zeolites—the study aims to provide a comprehensive un- because clearly defned local chemical bonds, either covalent
derstanding of the adsorption mechanisms involved. Fur- or supramolecular, are formed [18]. For a particular ad-
thermore, the exploration of modifed zeolites introduces sorbent material, the various interactions will depend on
a dimension of tailoring adsorption properties, demonstrating factors such as the compounds’ solubility, the quantity of H-
the versatility of zeolites as adaptable materials for addressing donor groups, and the acid-base properties [19]. Recent
specifc environmental challenges [17]. Te present study aims research showed that drugs adsorbed from aqueous solu-
at investigating the sorption mechanisms of selected organo- tions on zeolites had stable H-bonded adducts [13].
chloride pollutants on diferent types of zeolites (245 types), Adsorption and degradation are two key processes in the
determining the infuence of zeolite properties (e.g., framework removal of organic pollutants from the environment using
structure, composition, surface chemistry) on the sorption of various materials [20]. Adsorption involves the physical or
organochloride pollutants, and exploring the potential of chemical adherence of pollutants to the surface of a solid
modifying zeolite surfaces through functionalization or in- material, increasing its concentration on the material’s surface.
corporation of additional materials to enhance the adsorption Tis is particularly relevant in high-porosity materials like ze-
capacity and selectivity for organochloride pollutants. Te olites, which ofer a large surface area for efective adsorption.
selection of organochlorides in this study is driven by their On the other hand, degradation refers to the transformation of
widespread environmental presence and persistence, posing pollutants into less harmful substances through chemical re-
risks to ecosystems and human health. Organochlorides, found actions, often facilitated by catalysts or reactive materials. Both
Journal of Chemistry 3

processes play crucial roles in environmental remediation, with Table 1: List of pollutants with their calculated zeolite-guest in-
adsorption providing immediate pollutant removal and deg- teraction energies for zeolite MOR and FAU obtained from
radation ofering a long-term solution by breaking down literature.
pollutants into less toxic forms. Te choice of materials, their MOR FAU
properties, and the specifc pollutants targeted are critical factors Pollutant
Ezg (kJ mol−1) Ezg (kJ mol−1)
infuencing the success of these processes. Acetaminophen −6 −12
Te strength and stability of the adsorption are de- Atrazine 43 2
termined by the zeolite-guest interaction energy, which is Cafeine 12 5
a critical factor in the adsorption process (Table 1). A Carbamazepine 40 11
stronger afnity between the zeolite and the organic pol- DEET 97 6
lutant is indicated by a higher interaction energy, which Diazepam 17 5
leads to a more efcient adsorption process. Te zeolite’s Diclofenac −15 −2
chemical makeup, the framework’s structure, the size and Dilantin 14 1
shape of the organic pollutant molecule, and the type of Estrone 100 35
chemical bonds that connect the zeolite and the pollutant Fluoxetine 100 98
Gemfbrozil 98 6
can all have an impact on the interaction energy. Designing
Hydrocodone 23 26
efective adsorbents for the removal of organic contaminants Ibuprofen 98 6
and optimizing adsorption procedures depend on an un- Meprobamate 97 7
derstanding of the zeolite-guest interaction energy [21]. Naproxen 82 2
Researchers can increase the adsorption capacity and se- Oxybenzone 99 47
lectivity of zeolites by adjusting the zeolite characteristics Pentoxifylline 21 3
and managing the interaction energy, leading to more ef- Sulfamethoxazole 13 0
fective methods for water purifcation and environmental TCEP 21 7
remediation. Triclosan 99 45
Te sorption and desorption processes are pivotal as- Trimethoprim 46 5
pects of the studied zeolite-based organochlorine adsorption
system. Te investigation into sorption involves un- implementation of zeolite-based remediation strategies.
derstanding how zeolites attract and retain organochlorine Table 1 shows a summary of various organic pollutants with
compounds, shedding light on the mechanisms governing their associated interaction energy as reported in the liter-
the initial uptake. Te zeolite’s microporous structure and ature for two zeolite types, MOR and FAU.
high surface area play a crucial role, providing ample sites for Molecular mechanical techniques enable atomic-level
the adsorption of organochlorines. Te simulations and analysis of materials and determination of bulk properties
experimental data collectively suggest that the adsorption using force felds [22]. Te interactions in a molecular system
process is infuenced by factors such as the type of zeolite, are determined by potential functions. A specifc instance of an
structural modifcations, and the specifc characteristics of adsorption process is represented by each model statement in
the organochlorine compounds. On the other hand, the statistical physics modeling. Tese models are developed
exploration of desorption is equally signifcant, as it ad- progressively, starting with the simplest Langmuir model (one
dresses the practical applicability and sustainability of site energy, one site occupation, and one layer) and progressing
zeolite-based remediation. Te ability to desorb and release to more complicated adsorption systems such as the Hill model
organochlorines from zeolites is vital for the regeneration (monolayer, monoenergy, and multioccupancy), double Hill
and reusability of the adsorbent material. Te study’s em- (monolayer, diferent site energies, and mono-occupancy), or
phasis on investigating desorption characteristics provides BET (multilayer, multisite energies, mono-, or multi-
valuable insights into the reversibility of the adsorption occupancy) [23, 24]. In order to choose the optimal material for
process. Factors afecting desorption efciency, such as adsorption of organochlorines (Figure 1) from water, this
temperature and pore structure, are crucial considerations research ofers a simulation-based method to forecast the
for optimizing zeolite regeneration. Te comprehensive loading ability of several zeolites. In order to determine the
nature of the study, incorporating both simulation and signifcance of the many descriptors that have an impact on the
experimental results, allows for a nuanced understanding of elimination of these organic pollutants from water, a data-
sorption and desorption dynamics. Te structural modif- based approach was used. Insights into the sorption mecha-
cations, including silicon, aluminum, or sodium doping, nisms were provided by quantum chemical simulations. Te
contribute to tailoring zeolite properties for enhanced impact of doping the zeolites with particular elements on the
sorption and desorption capabilities. Tis strategic approach loading capacity was then thoroughly examined. Laboratory
aligns with the goal of developing efcient and sustainable experiments were performed using adsorption columns, and
environmental remediation technologies. In essence, the the role of interstitial water was established.
discussion on sorption and desorption in this study high- Tis comprehensive study on the adsorption capacities
lights the multifaceted nature of zeolite-organochlorine of various zeolites for selected organochlorines, Figure 1,
interactions. It underscores the importance of not only ef- holds signifcant importance in the feld of environmental
fective adsorption but also the ability to release contami- science and material engineering. Te research not only
nants, providing a holistic perspective on the practical provides detailed insights into the structural characteristics
4 Journal of Chemistry

Hexachlorobenzene (HCB) Hexachlorotetradecane (HCTD) Hexachlorodecane (HCD)

Hexachlorocyclohexane (HCH) Heptachlorodecane (HPCD) Octachlorodecane (OCD)

Dichlorodiphenyl trichloroethane (DDT) Heptachlorotetradecane (HPCTD) Octachlorotetradecane (OCTD)

Figure 1: Examples of chlorinated organic pollutants that have been reported in surface and underground waters.

and performance of diferent zeolites but also establishes trials, operations of translation, rotation, regeneration,
a correlation between their properties and adsorption ca- CFCMC interchange of “fractional” particles, and identities
pacities. Te identifcation of the universal force feld as the adjustments. Whole adsorption isotherms were calculated
most suitable for predicting adsorption behaviors enhances for each chlorinated compound. Material Studio software
the understanding of molecular interactions. Moreover, the was used for all simulations [32]. Te IRASPA software [33]
investigation into the impact of zeolite doping on adsorption was used to quantify the characteristic features of zeolites,
capacity, supported by thorough analysis and charge dis- including mass (M), density (D), helium void fraction
tribution studies, adds a valuable dimension to the study. (HVF), accessible pore volume (APV), gravimetric surface
Te laboratory experiments, particularly the comparison area (GSA), and dimensionality of the pore system (Di). To
between treated and untreated zeolites, reveal practical investigate the efect of silicon, aluminum, or sodium doping
implications for zeolite application in pollutant removal. Te in the CLO zeolite, fve phosphorus atoms were replaced
fndings emphasize the critical role of oxygen atoms in with silicon, aluminum, or sodium. In each case, an extra
creating active adsorption sites, shedding light on a key framework was created in order to balance the charges. After
structural feature infuencing adsorption efciency. Gen- this, new charges were assigned on all the atoms both in the
erally, this research contributes to the optimization of zeolite zeolite structure and the extra framework created.
selection and treatment methods for environmental re- Clinoptilolite and faujasite zeolites were obtained
mediation, ofering valuable insights for designing efective commercially for experimental use. Before sorption exper-
adsorbents in pollution control applications. iments, the zeolites were activated by heating at high
temperatures of 400°C under vacuum pressure for 24 hrs.
2. Materials and Methods Te experimental setup was meticulously designed,
employing columns as the primary vessels for adsorption.
Te International Zeolites Association (IZA) database Tese columns were flled with various adsorbents, which
provided all of the zeolites used in this simulation work [25]. were compacted using distilled water [34] to ensure con-
Te structures for the organochlorines were obtained from sistency in the packing density. Two diferent types of zeolite
PubChem [26] and optimized using the Dmol3 module adsorbent materials were used, faujasite zeolite (zeolite x)
program [27] in material studio software [28] using the and clinoptilolite, for comparison purposes. To enhance the
GGA/PBE functional [29] and DND basis set [30]. Grand- hydrophobic nature and Si/Al ratio of zeolite x, a mixture
canonical Monte Carlo (GCMC) simulations were carried with silica gel in a specifc ratio (5 : 3) was prepared. Tis
out utilizing the continuous fractional component approach careful manipulation aimed to optimize the adsorption ef-
(CFCMC) to explore adsorption [31]. Mostly in the grand- fciency of zeolite x when utilized in the columns. Tis was
canonical ensemble, the chemical potential, volume, and done for both treated and untreated zeolite. Simultaneously,
temperature remain constant. Te frugality coefcients were clinoptilolite, known for its Si/Al ratio ranging between 4.0
taken to be 1. Every location on the adsorption isotherms and 5.3 [35], was investigated independently. Silica gel,
was created using production cycles 5 × 105. Each Monte a material with potential adsorption capabilities for organic
Carlo cycle was performed using the random Monte Carlo pollutants, was also included in the experimental design for
Journal of Chemistry 5

comparison purposes. Te experimental apparatus com- organometallic systems and other systems for which other
prised fve columns: one contains silica gel, another with force felds do not have parameters [40]. As a result, we
treated zeolite x, a third with untreated zeolite x, the fourth concentrated on the universal force feld in the primary text.
with treated clinoptilolite, and the ffth with untreated cli- Table S1 (supporting information) displays the structural
noptilolite zeolite. A meticulous calibration process was characteristics of 245 diferent types of zeolites along with
implemented using various standard solutions derived from the loading of HCB, including mass (M), density (D), helium
a 30 ppm stock solution of the hexachlorobenzene pollutant. void fraction (HVF), accessible pore volume (APV),
Each column was flled with a predetermined amount of gravimetric surface area (GSA), and dimensionality of the
water to establish the initial pollutant concentration. Te pore system (Di). Out of the 245 zeolites that were studied,
pollutant solution, with a known concentration of 15 ppm, 71 zeolites demonstrated the ability to adsorb hexa-
was systematically passed through each column. Filtrate chlorobenzene with CLO, a cubic microporous gallophos-
concentrations were confrmed through multiple iterations, phate with three-dimensional channels surrounded by 20-
providing a comprehensive dataset for determining equi- membered rings in the shape of a four-leaf clover, having the
librium concentrations and evaluating the reusability of each highest capacity of 65.84 wt%. CLO showed a stepwise
zeolite under diferent conditions. multilayer adsorption isotherm that only occurs when the
sample surface has various adsorption site types with en-
3. Results and Discussion ergetically diverse properties (Figure 4).
Conversely, the loading of all the other zeolites was
3.1. Simulations of Organochlorine Adsorption Mechanisms to relatively low with nearly a horizontal plateau isotherm. Tis
Zeolites. Te structures of selected organochlorines (Fig- is attributed to the limited active sites for HCB adsorption.
ure 1) were optimized and their Frontier molecular orbitals CLO has a mass of 17728 g/mol, density of 1129 kg/m3,
were calculated (Figure 2). Te global hardness, calculated helium void fraction of 0.55, a dimensionality of the pore
using the HOMO energy of the orbital (EHOMO ), is fre- system of 3, a largest overall cavity diameter of 15.33, and
quently connected with a molecule’s capability of donating a larger volumetric surface area of 1070 m2/cm3. On the
electrons, while the LUMO energy of the orbital (ELUMO ), other hand, RWY has a lower mass and density (2884 g/mol
depends on the molecule’s capability to accept electrons. Te and 1129 kg/m3, respectively) and a higher helium void
diference in energy between HOMO and LUMO also fraction, accessible pore volume, and gravimetric surface
contributes to the explanation of the electrical and chemical area (0.66 and 0.77 cm3/g, respectively) compared to CLO. It
properties of the particles. Hexachlorodecane possesses the has a comparable volumetric surface area with respect to
smallest HOMO energy (−0.2558 eV), but dichlor- CLO. It has 54.23 wt% of hexachlorobenzene and is ranked
odiphenyltrichloroethane has a considerably greater HOMO the second after CLO in terms of wt%. ITV is ranked the
energy (−0.1832 eV), as determined by analyses of the third after RWY. Despite ITV having a larger mass, density
electron orbitals energy levels. Te HOMO-LUMO energy and VSA than RWY, it possesses a lower HVF, APV, GSA,
gaps are 0.1456, 0.1952, 0.1841, 0.1777, 0.1912, 0.1761, 0.1406, and Di compared to RWY. Tese diferences may be used to
0.1696, and 0.1977 eV for hexachlorobenzene, hexa- explain why it has 33.65 wt% compared to 54.23 wt% of
chlorotetradecane, hexachlorodecane hexachloro RWY. ITV is followed closely by IFU which has adsorption
cyclohexane, heptachlorodecane, octachlorodecane, capacity of 32.41% wt. IFU has a small mass, HVF, APV,
dichlorodiphenyltrichloroethane, heptachlorotetradecane, VSA, and GSA compared to ITV. Tis may be the reason
and octachlorotetradecane, respectively. Terefore, octa- why it has a lower capacity than ITV. However, IFU has
chlorotetradecane has a higher stability. It has relatively a larger Di than ITV and this explains why it ranked after
a higher chemical hardness of 0.1977 eV, while dichlor- ITV. LTA has almost similar loading capacity as IFU
odiphenyltrichloroethane is less stable and has a relatively (32.31 wt% vs. 32.41 wt%, respectively). Tis closeness may
low chemical harness of 0.1406 eV. be attributed the closeness in VSA and Di between the two
Considering the structure of HCB (a phenyl ring with six zeolites. However, LTA has a lower mass than HVF, APV,
chlorine atoms attached on each of the carbon atoms), we and GSA and this explains why it has a lower capacity for
frst evaluated its adsorption capacities on the zeolites. HCB than IFU. On the other hand, zeolite LTA has a higher
Materials Studio software has a variety of inbuilt force felds density than IFU and this may be an attribute as to why it
which are designed for the adsorption of diferent categories ranked ffth after IFU. Zeolite IRR has a higher mass than
of compounds. Tus, we frst compared the outcomes of HVF, APV, GSA, and Di. It is expected that it has a higher
several force felds (Figure 3), in order to choose a force feld capacity than LTA. However, this is not the case; instead, it
that is appropriate for our systems. has a lower wt% capacity than LTA. It has 31.31 wt%
In contrast to compass [36], valency-consistent force compared to 32.31 wt% of LTA. Tis scenario might have
feld, CVFF [37], and polymer-consistent force feld, PCFF occurred due to the fact that zeolite IRR has a lower density
[38], we discovered that the universal force feld [39] was and VSA compared to LTA. Zeolites FAU, SBT, and VFI are
best for organic compounds used in this investigation. Since among those with similar HCB adsorption capacity, with
the geometries and conformational energy diferences of 28.32 wt%, and it may be attributed to their negligible dif-
organic molecules, main-group inorganics, and metal ferences in HVF, APV, and Di. In addition, they have almost
complexes have been found to be predicted with moderate equal densities and VSA. On the other hand, zeolite TSC has
accuracy by the universal force feld, it is suggested for the largest mass, density, and Di and yet it has a lower wt%
6 Journal of Chemistry

-0.2341 -0.2558
HOMO -0.2294 ΔE = 0.1952 ev
ΔE = 0.1841 ev
ΔE = 0.1456 ev -0.0389 -0.0717
-0.0838
LUMO

(a) (b) (c)

HOMO -0.2495
-0.2553 -0.2427 ΔE = 0.1761 ev
ΔE = 0.1777 ev
ΔE = 0.1912 ev
-0.0776 -0.0734
LUMO -0.0515

(d) (e) (f )

HOMO

-0. 1832
-0.2388 -0.2395
ΔE = 0.1406 ev
ΔE = 0.1696 ev ΔE = 0.1977 ev
-0.0777
LUMO -0.0692 -0.0418

(g) (h) (i)

Figure 2: Optimized structures of hexachlorobenzene (a), hexachlorotetradecane (b), hexachlorodecane (c) hexachlorocyclohexane
(d), heptachlorodecane (e), octachlorodecane (f ), dichlorodiphenyltrichloroethane (g), heptachlorotetradecane (h), and octa-
chlorotetradecane (i), respectively. Te colors gray, white, and green, respectively, represent the atoms of carbon, hydrogen, and chlorine.
Positive and negative orbital values are represented by the yellow and blue sections, respectively.

HCB capacity. In comparison with CLO, TSC would be adsorption capacity less than 1 wt%. All the other zeolites
expected to have a higher percentage capacity considering among the 71 had capacities above 5 wt%. A correlation
mass, density, and Di. However, the opposite is seen for HCB analysis was done in order to get more understanding of how
loading. Tis may be attributed to low HVF, APV GSA, and various structural features afect the wt% (Figure 5). Te
VSA in TSC zeolite. Among the 71 zeolites that showed the results showed that the mass of the zeolites and density were
possibility of adsorbing HCB compounds, eight of them had negatively correlated to adsorption capacity. Tis means that
an adsorption capacity less than 5 wt% with two having an a heavier material would have less uptake capacity compared
Journal of Chemistry 7

17
120
16
100
15
Loading of HCB on FAU

Loading of HCB on CLO

14 80

13 60
12
40
11
20
10

9 0
200 400 600 800 1000 200 400 600 800 1000
Fugacity Fugacity

Universal pcff Universal pcff

COMPASS vcff COMPASS vcff
Dreiding Dreiding
(a) (b)

Figure 3: Loading of hexachlorobenzene (HCB) molecules on FAU and CLO zeolites using various force felds.

investigated using a cluster model (shown in Figure 6). At

the level of DFT theory, the cluster was optimized. HCB was
20
added to the system and optimized after the cluster model
had been optimized. We hypothesized that HCB could
adsorb on the CLO cluster dissociatively by transferring a Cl
atom to the cluster, or HCB could adsorb to the cluster
Loading per cell

through hydrogen bonds. As seen in Figure 6, it is ther-

modynamically favorable for HCB to adsorb through hy-
10 drogen bonding as opposed to dissociative adsorption. As
can be seen in Table 2, we also looked at the Mulliken charge
distribution on HCB both before and after it bound to the
CLO zeolite cluster. According to the fndings, the chlorine
atoms in the HCB structure have an electron charge of −0.06,
0 whereas the carbon atoms have an electron charge of
0.06 each.
200 400 600 800 1000 Tus, before adsorption, the chlorine molecule has a net
Fugacity (KPa) zero charge. It is noteworthy to observe that upon ad-
sorption, there was a charge transfer between CLO and HCB,
CLO IRY RWY giving the chlorine atoms a new charge of −0.037, −0.061,
ITV SBT SBS −0.057, −0.055, −0.052, and −0.056, while the carbon atoms
FAU IFT SYT
have a charge of 0.055, 0.053, 0.054, 0.053, 0.050, and 0.054.
Figure 4: Adsorption isotherms, showing the adsorption of HCB Te net charge on HCB becomes 0.001. Te CLO cluster, on
on the selected best performing zeolites. the other hand, has a charge of 0.002 before adsorption. It
attains a charge of 0.001 after adsorption. According to the
to a lighter material. On the other hand, HVF, APV, VSA, Mulliken charge values, there is a charge transfer from HCB
GSA, and Di are positively correlated to wt%. However, to the CLO zeolite.
there is a strong positive correlation between APV and wt% An investigation was done into how doping CLO zeolite
compared to other parameters with a positive correlation. afects loading capacity (Table 3). Te phosphorus atoms are
Tis implies that accessible pore volume plays a key role to independently substituted with silicon, sodium, and alu-
the adsorption capacity of organochlorides on zeolites. Tis minum at diferent locations with varied symmetrical
information is key to the engineering of materials to suit the properties in the CLO unit cell, and optimization is then
applications in diferent felds. performed. It is noteworthy to notice that the loading of
Small cluster models have been applied by numerous hexachlorobenzene increases from 120 to 133, 126, and 127
research teams to zeolites [41-42]. In this work, the in- molecules per cell, respectively, when CLO is doped with
teraction of organochlorides with the zeolite framework was aluminum, sodium, and silicon, respectively. It is noted that
8 Journal of Chemistry

60 60

Adsorption capacity (wt%)

Adsorption capacity (wt%)
50 50

40 40

30 30

20 20

10 10

0 0
20000 40000 60000 80000 800 1000 1200 1400 1600 1800
Mass (g/mol ) Density (Kg/m3)
(a) (b)

60 60

Adsorption capacity (wt%)

Adsorption capacity (wt%)

50 50

40 40
30 30
20 20
10 10
0
0.3 0.4 0.5 0.6 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Helium void fraction (HVF) Accessible pore volume (APV)
(c) (d)

60 60
Adsorption capacity (wt%)
Loading capacity (wt%)

50 50

40 40

30 30

20 20

10 10

800 1000 1200 1400 1600 1800 2000 2200 500 1000 1500 2000 2500
Volumetric surface area (VSA) Gravimetric surface area (GSA)
(e) (f )

60 60
Adsorption capacity (wt%)

Adsorption capacity (wt%)

50 50

40 40

30 30

20
20
10
10
0
0 2 0 2 4 6 8 10 12 14 16
Dimensionality of pore system (DPS) Overall largest cavity diameter (Di)
(g) (h)

Figure 5: Correlation between zeolites structural parameters; M, D, HVF, APV, VSA, GSA DPS, Di, and adsorption capacity (wt%).
Journal of Chemistry 9

O +

P
Ga
ΔE = 0.02 Ha

0.00

ΔE = -0.04 Ha
Cl

Figure 6: Structures of optimized CLO cluster and adsorbed HCB molecules on the CLO cluster.

Table 2: Mulliken charge distribution on HCB, CLO, and HCB-CLO.

HCB (before adsorption) CLO before adsorption HCB–CLO after adsorption
C 0.6 Ga 1.296 Ga 1.295
C 0.6 P 1.582 P 1.579
C 0.6 O −0.817 O −0.816
C 0.6 O −0.742 O −0.757
C 0.6 O −0.761 O −0.742
C 0.6 O −0.752 O −0.754
Cl −0.6 O −0.74 O −0.75
Cl −0.6 O −0.695 O −0.701
Cl −0.6 O −0.744 O −0.75
Cl −0.6 Ga 1.298 Ga 1.304
Cl −0.6 P 1.579 P 1.582
Cl −0.6 O −0.815 O −0.818
O −0.76 O −0.739
O −0.744 O −0.741
O −0.754 O −0.745
O −0.76 O −0.759
O −0.699 O −0.698
O −0.748 O −0.757
P 1.585 P 1.58
P 1.578 P 1.583
Ga 1.301 Ga 1.29
O −0.698 O −0.696
O −0.753 O −0.749
O −0.743 O −0.755
O −0.697 O −0.69
O −0.816 O −0.815
Ga 1.288 Ga 1.287
O −0.816 O −0.817
C 0.055
C 0.053
C 0.054
C 0.053
C 0.05
C 0.054
Cl −0.037
Cl −0.061
Cl −0.057
Cl −0.055
Cl −0.052
Cl −0.056
10 Journal of Chemistry

Table 3: Efect of doping on adsorption capacity of CLO zeolite.

Doping atom Loading Wt% Energy (kcal/mol) Isosteric heat (kcal/mol)
Al 133 68.0 −341.178 44.892
Si 127 67.0 −360.479 127.000
Na 126 67.0 −362.833 44.992

doping CLO zeolite provides improved results in terms of (Table S2). Te best zeolite for adsorption of hexa-
both loading and wt%, whereby aluminum provided the best chlorodecane is CLO which has 47 molecules per cell an
results (Table 3). Te energy diference between the reactants equivalent of 46 wt%. Tis is followed by TSC, FAU, ITV,
adsorbed states upon doping was also investigated (Fig- IFT, RWY, IRY, SBT, and SBS, respectively. Finally, CLO is
ure 7). Tis was done by substituting phosphorus atom with still the best adsorbent for heptachlorodecane adsorption
a single aluminum atom in the CLO cluster. Contrary to the with 30 molecules per cell. Te adsorption isotherms rep-
undoped case, it is thermodynamically favorable for HCB to resenting this information are shown (Figure 8). Te shapes
adsorb through dissociative adsorption as opposed to of these fgures can be used to inform us that the zeolites
through hydrogen bonding. It is also worth noting that studied have diferent distribution of active sites for ad-
doping increases the system energy, i.e., 0.02 verses −12.25 sorption of the selected organic compounds. However, it is
and −0.04 verses −12.63 Ha for the undoped and doped evident that CLO zeolite has more active sites as seen from
zeolites, respectively. its adsorption isotherm. It is important to note, from these
Te efect of Al doping on Muliken charge distribution isotherms, that there are diferent sites on each zeolite with
was investigated (Table 4). Te charge on each atom before diferent energy requirement leading us to stepwise iso-
and after adsorption was calculated as 0.060 on each carbon therm. Tis applies to all zeolites studied (See Figure 8). Tis
atom and −0.060 on each chlorine atom before adsorption, fnding led us into investigation to fnd out about these active
while −0.001, −0.001, 0.000, −0.009, −0.036, and −0.002 for sites. Adsorption locator module was thus used to identify
carbon atoms and 0.072, 0.031, 0.033, 0.028, 0.024, and 0.028 the adsorption sites as seen in Figure 9. It is noted that the
for chlorine atoms after adsorption. While HCB has a zero organic compounds are adsorbed through electrostatic in-
charge before adsorption, after adsorption, HCB molecule teraction within the zeolite structure. However, in this case,
inside the zeolite becomes positively charged with a net oxygen atoms provide active interaction sites. It is indicated
charge of 0.167. On the other hand, a doped CLO cluster is that the pores surrounded by more oxygen atoms are the
positively charged with a charge of 0.001 before adsorption. most preferred. Tus, afnity for organic pollutants can be
After adsorption, it acquires a −0.096 net charge, making it increased by increasing the number of oxygen atoms.
negatively charged. According to these Mulliken charge Te performance of CLO zeolite over other zeolite
values, charge transfer from HCB to the CLO zeolite takes materials enabled an investigation to fnd out possible
place, similar to the undoped scenario, and thus it is noted features responsible for its best performance. Previously, it
that doping does not alter the charge transfer pattern. has been reported that various general structural features
For comparison, we also looked into the adsorption of have an impact on sorption ability of zeolites [43-44].
hexachlorocyclohexane (Table S2), dichlorodiphenyltri- However, few reports have focused on how sorption per-
chloroethane (Table S3), hexachlorotetradecane (Table S4), formance is infuenced by the structural composition of
heptachlorodecane (Table S5), octachlorodecane (Table S6), zeolites [44]. We therefore investigated the distribution of
hexachlorodecane (Table S7), heptachlorodecane (Table S8), active adsorption sites on the surfaces of the zeolites which
and octachlorobenzene (Table S9). It is observed that for facilitated the afnity for organic compounds. Since most of
hexachlorotetradecane, CLO zeolite was also the best with the zeolites have oxygen atoms in their framework, it was
a loading capacity of 21 molecules per cell. Tis is equivalent very necessary to fnd out the infuence of these atoms to
to 31 wt%. Tis is followed by ITV, TSC, FAU, IFT, IRY, adsorption capacity. Interestingly, it was discovered that
RWY, SBT, and SYT, respectively. For hepta- oxygen atoms played a key role in active sites provision. Tis
chlorotetradecane, CLO is still the best adsorbent with 22 implies that the more the oxygen atoms, the more the active
molecules adsorbed per cell, which corresponds to 36 wt%. sites on the zeolite surface, and hence more adsorption
Tis is followed by ITV, FAU, IRY, SBT, IFT, RWY, SBS, and capacity. Table 5 shows a summary of the adsorption ca-
SYT. Octachlorotetradecane also exhibits CLO as the ad- pacity versus the number of oxygen atoms.
sorbent with 17 molecules per cell. Tis is equivalent to 38 wt
%. It is followed by TSC, ITV, FAU, RWY, IRY, IFT, SBT,
DFO, and EMT, respectively. Dichlorodiphenyltrichloro- 3.2. Laboratory Adsorption Experiments of Organochlorines
ethane still exhibits CLO as the best candidate for its ad- on Zeolites. Zeolites treatment is one of the key practices
sorption with an uptake capacity of 43 molecules per cell. performed in order to activate them prior to any application
After CLO, TSC, ITV, FAU, RWY, IRY, IFT, SBT, DFO, and [54]. One of the reasons why zeolites are treated is to remove
EMT show good adsorption capacities. On the other hand, interstitial water from their framework. Tere are several
hexachlorocyclohexane adsorbs on CLO with 113 molecules zeolites treatment methods that have been employed in
per cell which is equivalent to 54 wt%, followed by TSC, ITV, previous studies [54-56]. Tese include heat treatment at
IFT, FAU, IRY, RWY, DFO, SYT, and LTA, respectively high temperatures and acid treatment methods among
Journal of Chemistry 11

O
Al

Ga P

0.00

E = -12.2513 Ha

Cl E = -12.6285 Ha

Figure 7: Optimized structures of Al-doped CLO cluster and HCB adsorbed on the doped cluster.

Table 4: Efect of Al doping on Mulliken charge distribution.

Al-doped CLO cluster before Al-doped CLO-HCB after
HCB (before adsorption)
adsorption adsorption
C 0.6 Ga 1.281 Ga 1.19
C 0.6 Al 1.157 Al 1.229
C 0.6 O −0.717 O −0.633
C 0.6 O −0.722 O −0.613
C 0.6 O −0.674 O −0.644
C 0.6 O −0.686 O −0.6
Cl −0.6 O −0.673 O −0.649
Cl −0.6 O −0.654 O −0.635
Cl −0.6 O −0.691 O −0.609
Cl −0.6 Ga 1.246 Ga 1.123
Cl −0.6 P 1.506 P 1.194
Cl −0.6 O −0.713 O −0.673
O −0.677 O −0.609
O −0.684 O −0.607
O −0.733 O −0.661
O −0.713 O −0.588
O −0.647 O −0.602
O −0.677 O −0.645
P 1.516 P 1.174
P 1.511 P 1.174
Ga 1.273 Ga 1.119
O −0.643 O −0.602
O −0.717 O −0.611
O −0.682 O −0.6
O −0.651 O −0.595
O −0.719 O −0.635
Ga 1.289 Ga 1.111
C −0.001
C 0.001
C 0.00
C −0.009
C −0.036
C 0.002
Cl 0.072
Cl 0.031
Cl 0.033
Cl 0.028
Cl 0.024
Cl 0.028
12 Journal of Chemistry

20 20
Loading per cell

Loading per cell

10 10

0 0

200 400 600 800 1000 200 400 600 800 1000
Fugacity (KPa) Fugacity (KPa)

CLO FAU RWY CLO IRY RWY

ITV IFT SBT ITV SBT SBS
TSC IRY SYT FAU IFT SYT
(a) (b)

20
Loading (per cell) 40
Loading per cell

10
20

0
0
200 400 600 800 1000 200 400 600 800 1000
Fugacity (KPa) Fugacity (KPa)

CLO IFT SBT CLO RWY SBT

ITV IRY EMT TSC IRY DFO
FAU RWY SBS ITV IFT EMT
FAU
(c) (d)
120

100 40
Loading (per cell)
Loading (per cell)

80

60
20
40

20

0
0
200 400 600 800 1000
200 400 600 800 1000
Fugacity (KPa)
Fugacity (KPa)
CLO FAU DFO CLO ITV IRY
TSC IRY SYT TSC IFT SBT
ITV RWY LTA FAU RWY SBS
IFT
(e) (f )
Figure 8: Continued.
Journal of Chemistry 13

30
20
25
Loading (per cell)

Loading (per cell)

20

15 10

10

5
0
0
200 400 600 800 1000 200 400 600 800 1000
Fugacity (KPa) Fugacity (KPa)

CLO IFT RWY CLO RWY SBT

ITV FAU SYT ITV IRY SYT
TSC IRY SBT FAU IFT EMT
(g) (h)

Figure 8: Adsorption isotherms for other chlorinated pollutants.

(a) (b)

Figure 9: (a) CLO zeolite framework. (b) Adsorption sites for hexachlorobenzene within the CLO zeolite.

others. In the current study, the efect of heat treatment at obtained from the column for analysis. On the other hand,
400°C to adsorption of chlorinated compounds was the sorption results for silica gel were not pronounced. Tis
investigated. therefore showed that silica gel could not adsorb organic
Since columns were used for adsorption experiments, pollutants but increased hydrophilic nature of zeolites
packing was done using distilled water by frst preparing (Table 7). Tis result closely agreed with the present liter-
slurry to facilitate compact packing. Te results showed that ature on the use of silica gel in adsorption [57].
the selected zeolites could not make slurry since they were Basing on the results obtained, it was discovered that the
highly hydrophobic. Tis hydrophobicity is attributed to untreated zeolite performed better than the treated one.
a low Si/Al ratio. Interestingly, it was discovered that the Si/ From Table 7 above, the treated zeolite adsorbed 3.2 ppm,
Al ratio could be improved by adding silica gel powder to the 0.3 ppm, 0.1 ppm, 0 ppm, and 0.2 ppm for the fve time runs,
zeolite in the ratio 3 : 5 (silica: zeolites). Tis was discovered respectively. Tis trend indicates that the treated zeolite
after several trials as shown in Table 6. could reach saturation point only after the third run, after
Te sorption results showed that clinoptilolite zeolite which no more pollutant could be adsorbed. Tis means that
could not be used in columns for adsorption since it caused if one were to re-use the adsorbent, then it could be used
logging in the columns. As such no solution could be three times before recovery is done. On the other hand,
 14

Table 5: Correlation of oxygen atoms in adsorbate to high pollutant loading rate.

Average adsorption energy
Pollutant Carbon atoms Chlorine atoms Zeolite No. of oxygen atoms Reference (oxygen atoms) Loading per cell
(kcal)
CLO 5152 [45] 120 −641
RWY — [46] 12 −98
Hexachlorobenzene 6 6 ITV 379 [47] 21 −130
IFU 260 [48] 13 −178
LTA 600 [49] 13 −229
CLO 5152 [45] 132 999
TSC 897 [50] 30 3
Phenanthrene 14 0 ITV 379 [47] 26 131
FAU 624 [51] 16 −3
IFT 317 [52] 16 −18
CLO 5152 [45] 21 −124
ITV 379 [47] 6 −46
Hexachlorotetradecane 14 6 TSC 897 [50] 5 −65
FAU 624 [53] 5 −95
IFT 317 [52] 5 −108
CLO 5152 [45] 19 −102
ITV 379 [47] 6 −10
Octachlorotetradecane 14 8 FAU 624 [51] 4 −74
IFT 317 [52] 4 −65
IRY 154 [46] 3 −39
Journal of Chemistry
Journal of Chemistry 15

Table 6: Determination of appropriate zeolite silica mixing ratio in Table 8: Te remaining hexachlorobenzene compound concen-
order to improve Si/Al ratio in the zeolite. tration after adsorption.
Amount Concentration
Amount of silica (g) Comment Material
of zeolite (g) 1 2 3 4 5
0.0 Hydrophobic Treated zeolite x 2.7149 2.3756 0.2262 0.2262 0.1131
0.1 Hydrophobic Untreated zeolite x 1.4706 0.9615 0.2262 0 ND
0.2 Hydrophobic Silica gel 4.4118 4.4118 4.2986 4.4118 4.2986
0.5
0.3 Hydrophilic
0.4 Hydrophilic
0.5 Hydrophilic zeolites for organic pollutant adsorption heavily depended
on the number of oxygen atoms present in the structure
(Table 5). Integrating these three simulation fndings with
Table 7: Hexachlorobenzene removal by faujasite zeolite and silica the experimental results, we found out that, heating the
gel for fve runs into columns. zeolite, apart from removing inorganic impurities, also
Amount removed (ppm) removes interstitial water from the zeolite framework. Tis
Material interstitial water within the zeolite structure contains the
1 2 3 4 5
hydroxyl radicals which are reactive with organic molecules.
Treated faujasite zeolite 3.2851 0.3393 0.149 ND 0.2149 Tey contain a negative charge which reacts with the positive
Untreated faujasite
5.3294 0.5091 0.7353 0.2262 ND charges in the compound (ion exchange). Tus, heating the
zeolite
Silica gel 0.5882 ND 0.1132 ND ND zeolite material reduces the value of negative hydroxyl ions
and therefore the reaction between the zeolite and the
ND � not detected.
positive organic compound reduces. Tis causes poor per-
formance of the heated zeolite and the better performance of
untreated zeolite adsorbed 5.3 ppm, 0.5 ppm, 0.7 ppm, and the untreated zeolite material. Secondly, since the in-
0.2 ppm for the fve run times, respectively. Tis trend is teraction mechanism involved between the zeolite and the
quite interesting in the sense that the material could not hexachlorobenzene is electrostatic through hydrogen
reach saturation after the fve re-uses. Tis is due to the fact bonding, heating reduces the number of hydrogen atoms in
that the remaining concentrations after the third run could the zeolite framework which could facilitate the interaction.
not be detected, implying that most the compounds had Hence, the untreated zeolite with more hydrogen atoms
been adsorbed and the material could still adsorb more. performs better. Finally, the simulation results indicated that
Table 8 shows the remaining concentrations after every run the active adsorption sites for organic pollutants under study
through the columns. In addition, the amount of compound were provided by the oxygen atoms. Since water molecules
adsorbed after every run through the columns was much compose of oxygen atoms, heating would mean removing
higher than that of treated zeolite. Previous researchers have more oxygen atoms from the framework. Terefore, there
explained the efect of various treatment methods to ad- would be less oxygen atoms which could bond with the
sorption of methylene blue. Hor and co-authors [58] re- chlorine atoms in the organochloride compounds (Figures 6
ported that both the physico-chemical methods of acid and 7). Tus, the treated zeolite adsorbs less than the un-
treatment and base treatment were able to boost the per- treated one. It is worth noting that the present fndings, both
formance of natural zeolite from 41% to 98.8%, and 52.2%, experimental and computational, have strongly agreed as
respectively. However, their report showed that combining discussed.
reduced performance would be observed when any of the Comparing our study with the previous study by Kul-
methods were combined. Tis shows that diferent treatment deyev et al. [59] on the adsorption of heavy metals on ze-
methods favor diferent adsorbates. Our present work olites, it noted that our fnding on the zeolite treatment
therefore reveals that thermal treatment as a method of methods contradicts what was suggested in their study. Te
zeolite treatment lowers the zeolite performance, as com- study focused on enhancing the adsorption capabilities of
pared to untreated zeolites. natural zeolites from the Shankanay deposit in Kazakhstan
Te percentage removal calculation reveals that un- for heavy metal ions in water. Te researchers employed
treated zeolite removes up to 91% of hexachlorobenzene. thermal methods to modify the zeolites and increase their
Comparing this experimental work with the simulated re- specifc surface area and porosity. Tree stages of activation
sults, we were able to fnd out that for organic pollutants, were conducted, involving cleaning the zeolites with water
untreated zeolites performs better than treated zeolite. Tis vapor, demineralization through acid treatment, and high
is based on the fact that, one, our computations of the thermal activation in an inert atmosphere. Te results
Mulliken charge analysis performed (Table 2) revealed that showed that thermal activation signifcantly improved the
there is charge transfer between the zeolite and organic adsorption capacity of the zeolites for various heavy metals.
pollutants during adsorption. Secondly, the interaction Te optimal condition was found to be a thermal treatment
mechanisms between the zeolite and hexachlorobenzene at 550°C for approximately 2 hours. Te heat-treated zeolites
involve electrostatic interaction through hydrogen bonding demonstrated high adsorption capacities, with percentages
(Figure 6), and thirdly, the number of active sites in the ranging from 83% to 100% for copper, cadmium, lead, and
16 Journal of Chemistry

nickel. Te adsorption process was found to be rapid, with helps us create more efcient methods for removing organ-
intense adsorption occurring within the frst 10 minutes. Te ochlorine pollutants from contaminated sites. Despite its
residual concentration of heavy metals in the fltered water value, the present study has a number of shortcomings that
remained within the permissible limits for drinking pur- need to be acknowledged. First of, the study was carried out
poses. Te study concluded that natural zeolites from the in a controlled laboratory setting, which might not accurately
Shankanay deposit have high potential as cost-efective refect the complexity of real-world settings. In addition, the
sorbents for the treatment of heavy-metal-polluted water, investigation of the kinetics of the process, which is essential
particularly in wastewater treatment and water softening for developing efective remediation solutions, was not done
applications in the metallurgical industry. Te fndings also as much in the study as it was largely on equilibrium ad-
suggested that thermal treatment may be more efcient than sorption. Te analysis of individual organochlorine com-
chemical treatment in enhancing the adsorption capacity of pounds also fails to take into account the occurrence of
zeolites, but further research is needed to confrm this. combinations in real-world situations, where many pollutants
However, this contradiction may be as a result of diferent may interact and compete for adsorption sites. Te re-
interaction mechanisms between the zeolite and the strictions on mass transfer, reactor design, and the behavior of
material. zeolite materials at greater scales may all provide difculties
for scaling up the fndings to broader uses. In addition, not
much study has been done on the long-term stability and
3.3. Factors Tat Afect Adsorption of Organochlorine Pol-
durability of zeolite materials, which is crucial for assessing the
lutants on Zeolites. Te outcomes of the current study may
viability and sustainability of zeolite-based remediation so-
be infuenced by a number of factors. Te zeolite’s own
lutions. By addressing these restrictions, future research will
characteristics, such as its surface area, pore size, surface
improve our knowledge and speed the creation of more ef-
charge, and composition, are important. Te adsorption
fcient and useful environmental cleanup technologies.
behavior can be afected by changes in the solution’s pH and
temperature, as well as the presence of other chemicals or
pollutants. Te molecular size and hydrophobicity of the 4. Conclusions
organochlorine compounds, as well as other physico- In this work, the investigation into organochlorine ad-
chemical characteristics, afect their adsorption afnity. Te sorption using zeolites, combining simulation and experi-
adsorption kinetics and achievement of equilibrium are mental approaches, has delivered impactful fndings.
infuenced by the contact time and agitation level. Important Simulation work utilizing the IZA database and PubChem,
factors to take into account also include the presence of rival along with GCMC simulations, deepened our understanding
chemicals and the capacity to regenerate and re-use zeolite of adsorption mechanisms. Material Studio and IRASPA
materials. For precise and dependable fndings in research software facilitated quantitative zeolite analysis. Experi-
involving the adsorption of organochlorine chemicals uti- mental validation with clinoptilolite and faujasite zeolites,
lizing zeolite materials, it is important to comprehend and subjected to strategic treatments, aligned with simulation
regulate these aspects. results, emphasizing the study’s robustness. Structural
modifcations, including silicon, aluminum, or sodium
3.4. Signifcance of Tis Study. Tis study has signifcant doping, and variations in the Si/Al ratio revealed their
consequences for environmental cleanup initiatives. It clarifes impact on adsorption efciency. Te inclusion of diferent
the adsorption mechanisms at work and shows the critical role zeolite types and silica gels for comparison enhanced
played by electrostatic interactions, particularly hydrogen practical relevance. Rigorous column adsorption tests and
bonding. Researchers can create more efective adsorbents for calibration curves provided quantitative insights. Tis study
removing organochlorines from contaminated settings based efectively bridges simulation and experimentation, high-
on this understanding. In addition, in order to help with the lighting zeolites’ adaptability in pollutant remediation. Te
selection of zeolites for particular remediation projects, the results afrm zeolites’ potential as versatile and sustainable
study compares the adsorption capacities of various zeolite materials for environmental applications, advancing the
materials and identifes certain zeolites with high adsorption understanding of their efcacy in water purifcation and
capacities for particular pollutants. Understanding how zeolite environmental protection.
structural characteristics afect adsorption performance might
help in the design and optimization of zeolite materials with Data Availability
improved qualities. Te study examines the efects of doping
zeolites with various elements and fnds that doping, especially Te research data used to support the fndings of this study
with aluminum doping, can increase loading capacity. Lastly, are included within the article and supporting information
the experiments show how crucial it is to take into account thereof attached.
how zeolite materials are treated, with untreated zeolite
exhibiting greater adsorption capacity and reusability. Col- Conflicts of Interest
lectively, these efects help us better understand how organ-
ochlorine adsorption operates, direct the design and selection Te authors declare that they have no conficts of interest
of zeolites, and ofer helpful tips for enhancing adsorption that could have appeared to infuence the work reported in
procedures in environmental remediation. Ultimately, this this paper.
Journal of Chemistry 17

Acknowledgments solutions on synthetic zeolites,” Microporous and Mesoporous

Materials, vol. 148, no. 1, pp. 174–183, 2012.
Te study was supported by the Austrian Partnership [14] H. M. Ötker and I. Akmehmet-Balcıoğlu, “Adsorption and
Programme in Higher Education and Research (APPEAR, degradation of enrofoxacin, a veterinary antibiotic on natural
Project 249). zeolite,” Journal of Hazardous Materials, vol. 122, no. 3,
pp. 251–258, 2005.
[15] C. E. Flores-Chaparro, C. Nieto-Delgado, and J. R. Rangel-
Supplementary Materials Mendez, “Hydrocarbons removal from water by carbon-based
See the supporting supplementary information for Tables S1 materials, macroalgae biomass, and derived composites,” in
Advanced Technologies in Wastewater Treatment, pp. 421–
to S9. (Supplementary Materials)
483, Elsevier, Amsterdam, Netherland, 2023.
[16] T. Manda, G. Baraza, and S. J. J. O. M. S. R. Omwoma,
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