Arabian Journal of Chemistry (2020) 13, 1945–1954

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
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ORIGINAL ARTICLE

Enhanced accessibility of active sites in hierarchical

ZSM-5 zeolite for removal of pharmaceutically
active substances: Adsorption and
microcalorimetric study
Vladislav Rac a,*, Vesna Rakić a, Dušan Stošić b, Vladimir Pavlović a,
Sanja Bosnar c, Aline Auroux d

a
Faculty of Agriculture, University of Belgrade, Nemanjina 6 Zemun, 11080 Belgrade, Serbia
b
Laboratoire Catalyse & Spectrochimie, UMR 6506, ENSICAEN, 6, boul. Mare´chal Juin, 14050 Caen, France
c
Ruder Bosˇkovic´ Institute, Division of Materials Chemistry, Bijenicˇka 54, 10000 Zagreb, Croatia
d
Institut de Recherches sur la Catalyse et l’Environnement de Lyon (IRCELYON), UMR 5256 CNRS/Universite Lyon1, 2
av. Albert Einstein, 69626 Villeurbanne Cedex, France

Received 9 January 2018; accepted 25 February 2018

Available online 14 March 2018

KEYWORDS Abstract The possibility of removal of pharmaceutically active substances, atenolol, diclofenac
Hierarchical ZSM-5; sodium and salicylic acid, from water solutions using hierarchical form of zeolite ZSM-5 is inves-
Pharmaceutically active tigated in this paper. Mesopore formation in ZSM-5 was achieved using alkaline treatment. Zeolitic
compounds; samples were characterized by X-ray diffraction, low temperature nitrogen adsorption, solid-state
Adsorption; 27Al MAS NMR, point of zero charge determination and microcalorimetry – volumetry of ammo-
Liquid calorimetry nia adsorption. Adsorption isotherms of pharmaceutically active substances were obtained and liq-
uid calorimetric experiments were used to evaluate the strength of interactions. The capacity for
salicylic acid adsorption measured for the mesoporous sample did not significantly differ from
the results obtained for the parent ZSM-5. However, in the case of atenolol and diclofenac sodium,
mesoporous ZSM-5 exhibited increased adsorption capacities. Calorimetric data revealed higher
heats of atenolol adsorption on mesoporous ZSM-5, compared to the parent. Based on similar acid-
ity and surface charge determined for the two samples, our results show that geometry and

Abbreviations: PAC, pharmaceutically active compound; CEC, contaminants of emerging concern; SA, salicylic acid; ATL, atenolol; DFC,
diclofenac-Na; pHpzc, point of zero charge; Qdiff, differential heat of adsorption
* Corresponding author.
E-mail address: vladarac@agrif.bg.ac.rs (V. Rac).
Peer review under responsibility of King Saud University.

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1946 V. Rac et al.

dimensions of both zeolite pores and adsorbing molecules play a crucial role in the studied adsorp-
tion processes and that tailoring ZSM-5 porosity by desilication can be used to expand its applica-
bility in depollution processes.
Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction hydrated aluminosilicates, which are well ordered in all three

dimensions: their cage-like structures usually have very high
Pharmaceutically active compounds (PACs) are substances internal and external surface areas of up to several hundred
commonly used in medicine, human and veterinary. During square meters per gram. They possess specific active sites that
their manufacture and use they can arrive in soil, surface waters might be active in adsorption. ZSM-5 zeolite is a medium-
and even in drinking water and are now considered an impor- pore zeolite with a three-dimensional interconnected channel
tant environmental threat (Wang and Wang, 2016; Kyzas system and 10-membered openings (5.1 Å
5.5 Å and 5.3 Å
et al., 2017; Daughton, 2016; Vasquez et al., 2014). The most
5.6 Å). The size of the channels intersection is close to 8.5–
important source of contamination is the pharmaceutical 9.0 Å (Ashtekar et al., 2000). Since the adsorptive capacities
industry; however, excretions from humans and animals are of zeolites can be limited by their pore sizes, the adsorption
also considered significant (Zhou et al., 2017; Corcoran et al., of the three pollutants on hierarchical ZSM-5 has been investi-
2010; Khetan and Collins, 2007; Prasse et al., 2010). Although gated in this work. Hierarchical zeolites are zeolites which,
the concentrations of PACs found in the environment are some- besides their inherent microporosity, also possess mesopores
times very low (Tambosi et al., 2010; Carballa et al., 2004; (Serrano et al., 2013; Schwieger et al., 2015). ZSM-5 zeolite
Garcia-Ac et al., 2009; Hollender et al., 2008), long-term expo- with hierarchical structure used in this investigation was
sure can lead to harmful effects. PACs are even classified as obtained by desilication procedure (Xiao et al., 2015; Mitchell
‘‘contaminants of emerging concern” – CECs (Daughton, and Pérez-Ramı́rez, 2011). Thus formed mesopores can be
2004) or ‘‘emerging pollutants”. Development of appropriate expected to be accessible to larger guest species, which might
methods for water pollution abatement caused by PACs is cur- extend the usability of the zeolite as an adsorbent. For that rea-
rently a topic which receives great scientific attention son, the adsorption capabilities of microporous and hierarchi-
(Glassmeyer et al., 2008; Rivera-Utrilla et al., 2013). Com- cal ZSM-5 zeolites toward salicylic acid, diclofenac sodium
monly used, filtration-based procedures are not completely suit- and atenolol were compared in this work. The adsorption of
able for removal of PAC molecules, which are usually polar and pollutants from aqueous solutions were studied by isothermal
of small dimensions. Since the pore sizes of either micro- or batch experiments and, additionally, using microcalorimetry
ultra filters are 100–1000 times larger, they allow pollutants to of adsorption in order to obtain both adsorption capacities
‘‘slip” through the membranes or filters (Deegan et al., 2011). and evaluate the corresponding strengths of adsorbate – adsor-
Therefore, it is not surprising that some of them can be found bent interactions. Changes in adsorptive properties were dis-
in drinking water from filtration plants (Khetan and Collins, cussed with respect to modifications of zeolite’s structure and
2007). Advanced oxidation processes (AOP) (Feng et al., acidity, which are induced by the introduction of mesopores
2013; Mohapatra et al., 2014; Marco-Urrea et al., 2010; Giri to its initially purely microporous structure. To the best of
et al., 2010; Klavarioti et al., 2009) have been studied, but AOPs our knowledge, such an investigation, which combines textural
can be expensive and energy consuming. Therefore, until pro- and surface characterization, quantitative acidity determina-
cesses leading to environmentally benign products are per- tion, batch adsorption investigation and, especially, liquid
fected, probing and improving different adsorbents will
remain in scientific focus (Papageorgiou et al., 2017; Lin
et al., 2015; Sathishkumar et al., 2015; Kyzas et al., 2013;
Ayranci and Duman, 2006; Polakovic et al., 2005) Our own
research (Rakić et al., 2015), concerning activated carbons as
adsorbents for PACs removal, revealed that the dominant fac-
tor influencing their adsorptive capacities was the magnitude of
their surface, while the strength of adsorbate, adsorbent inter-
actions was determined by the acidity/basicity of both the car-
bon surfaces and the pollutant molecules. Hence, another type
of materials, zeolites, which possess both acidic properties and
high surfaces, are the obvious choice for further investigations.
In this work, the results related to adsorptive properties of
synthetic zeolite ZSM-5 (in microporous and microporous/
mesoporous forms) for the removal of three PACs (salicylic
acid, diclofenac sodium and atenolol) from aqueous solutions
are reported. Zeolites are well known for their adsorptive capa-
bilities and their use for removal of pharmaceuticals from water
solutions has been studied (Martucci et al., 2012; De Ridder Fig. 1 Chemical structures of the investigated molecules: (a)
et al., 2012; González-Ramos et al., 2014). Zeolites are salicylic acid, (b) diclofenac sodium and (c) atenolol.
Enhanced accessibility of active sites in hierarchical ZSM-5 zeolite 1947

phase microcalorimetry of adsorption is applied for the first of KNO3 solutions (0.1 M and 0.01 M) were prepared, each
time in hierarchical zeolite – PACs interaction studies. solution having a different pH value (pHi), which was adjusted
All chemicals chosen to be adsorbed on ZSM-5 zeolite are by addition of 0.1 M HNO3 or 0.1 M KOH. 100 mg of a zeo-
recognized as emerging contaminants of water: salicylic acid litic sample was added to 50 ml of each solution and the mix-
(SA), diclofenac-sodium (DFC), a frequently used non- tures were then stirred for 24 h at room temperature. The solid
steroidal anti-inflammatory drug and atenolol (ATL), a beta- was separated from the solutions by centrifugation at 13,400
blocker drug. The reasons for the choice of these PACs are: rpm during 20 min and the final pH values (pHf) of the solu-
(1) their presence in industrial wastewaters, (2) their molecular tions were measured. The point of zero charge was determined
structures: different molecular sizes of the three molecules as the pH value at which a plateau is obtained on the graph
(Fig. 1) and their acidic/basic properties, which enable the pHf = f(pHi). Acidity of the samples was investigated by
investigation of the influence of both mesopore formation in microcalorimetric – volumetric measurements of ammonia
ZSM-5 and the zeolite’s acidity on its adsorptive capabilities adsorption. The heats of ammonia adsorption were measured
towards selected PACs. in a heat-flow Tian-Calvet calorimeter (Setaram), linked to a
glass volumetric line. Heats of adsorption and adsorption iso-
2. Experimental section therms were determined, using a well-established method
(Solinas and Ferino, 1998).
2.1. Materials
2.3. Adsorption measurements and liquid phase
Parent ZSM-5 zeolite, with SiO2/Al2O3 ratio of 50, was sup- microcalorimetry
plied by Zeolyst (CBV5524G). Salicylic acid (SA) and atenolol
(ATL) were supplied by pharmaceutical company ‘‘Galenika”, Adsorption of salicylic acid, diclofenac-Na and atenolol was
Belgrade, Serbia, and diclofenac-Na (DFC) was purchased studied using batch method (Damjanovic et al., 2010): approx-
from Sigma, Aldrich. imately 50 mg of a sample was mixed with an appropriate vol-
Mesopore formation in ZSM-5 zeolite was achieved via ume of adsorbate solution in a sealed container using a
alkaline treatment, using the method of Groen et al. (2004a, magnetic stirrer during 1 h at 303 K. Solid adsorbent was sub-
2004b). Zeolite samples (5 g) were subjected to NaOH solution sequently separated from aqueous solution by centrifugation
(0.2 M. 150 ml) during 30 min at the temperature of 333 K. (Minispin, Eppendorf, 13,400 rpm, 0.5 h). Equilibrium adsor-
Subsequently, the samples were filtrated, thoroughly washed bate concentrations were measured using spectrophotometry
with deionized water until a neutral pH was reached and dried (Shimadzu UV-1650PC). The adsorbed amounts (mol per
at 393 K overnight. Following the alkaline treatment, an acidic gram of zeolite) were determined as the difference between
treatment was preformed, using hydrochloric acid (0.1 M, 150 the initial and equilibrium concentrations. Every point of an
ml) for 6 h at room temperature. The samples were then fil- isotherm was obtained from a separate experiment. Measure-
tered, washed and dried again. Both parent and modified ments were done in triplicates. Initial solution concentrations
ZSM-5 were afterwards converted to their ammonium form were in the range 105 M to 103 M. The one hour equilibrium
by three-fold ion-exchange (150 ml, 0.1 M ammonium nitrate adsorption time was determined experimentally: for a fixed
at 363 K during 1 h). As prepared materials were filtered, dose of an investigated adsorbate, adsorbed amounts were
washed with deionized water and dried in an oven at 393 K. measured for different solid-liquid contact durations (15 min,
The resulting samples were calcined in air at 773 K, for 5 h. 30 min, 1 h, 2 h and 6 h). The values of concentrations that
were found remaining in solutions after 2 h or 6 h of stirring
2.2. Characterization were found to be the same as in the case of 1 h long contact
time.
Powder X-ray diffraction patterns were recorded on a Bruker Experimental data were fitted to the Langmuir, Freundlich,
(Siemens) 5005 diffractometer at room temperature using Cu Sips and Toth equations using Microcal Origin 8 software; the
Ka radiation (0.154 nm), from 3 to 80 2h in 0.02° steps, with corresponding constants were calculated. Eqs. (1)–(4) present
1 s per step. Nitrogen adsorption was performed at 77 K; zeo- Langmuir, Freundlich, Sips and Toth equations, respectively
lite samples were pretreated in vacuum at 673 K for 4 h. BET (Jaroniec and Marczewski, 1984):
and t-plot methods were used to calculate the textural proper- Sm KL ceq
Se ¼ ð1Þ
ties. Transmission electron Microscopy (TEM) was carried out 1 þ KL ceq
in a JEOL JEM-1400 Plus microscope operated at 120 kV. The
sample was dispersed from ethanol onto a carbon-coated cop- Se ¼ KF cneq ð2Þ
per grid which was subsequently dried at room temperature.
Solid-state 27Al MAS NMR spectra were acquired on a Bruker Sm ðKS ceq Þn
MSL-400 (9.39 T) spectrometer upgraded with Apollo console Se ¼ ð3Þ
1 þ ðKS ceq Þn
(Tecmag, USA) operating at 104.27 MHz. MAS probes (7
mm) were used and the spinning speeds were 4.7 kHz. Sm KT ceq
Single-pulse excitations of 2 ls were used for the 27Al MAS Se ¼  1=n ð4Þ
NMR experiments. All the spectra were accumulated with a 1 þ ðKT ceq Þn
3 s recycle time. Obtained chemical shift was determined in where ceq is the equilibrium concentration of adsorbate
ppm relative to AlCl3 6H2O solution as an external standard. (mol L1) and Se is the adsorbed amount at equilibrium
Point of zero charge for both samples was evaluated using (mol g1). In Langmuir, Sips and Toth equation Sm is the
batch equilibrium method (Dakovic et al., 2010). Two series maximum amount of adsorbate bonded (mol g1) and KL,
1948 V. Rac et al.

KS and KT are constants related to the energy of adsorbent –

adsorbate bonding. Constant n in Sips and Toth models is
related to the heterogeneity of the adsorption sites. If n = 1
Eqs. (3) and (4) reduce to Langmuir model, for which an ener-
getically homogeneous surface is postulated.
The heats of adsorption of investigated adsorbates were
determined using liquid calorimetric measurements. A differ-
ential heat flow reaction calorimeter (TITRYS, from
Setaram) equipped with a stirring system was used. The
calorimeter was linked by capillary tubes to a system for liq-
uid injection (a programmable syringe pump PHD 2000, from
Harvard Apparatus). Successive pulse injections of 0.2 ml of
adsorbate solutions were sent to the sample in 2 h time inter-
vals. The temperature of the calorimetric cell was maintained
at 303 K. Furthermore, each dose of the liquid was equili-
brated at the same temperature in a preheating furnace prior
to being injected in order to avoid enthalpy effects due to
mixing phenomena. All liquids used in this investigation were
previously purged with flowing nitrogen as this procedure, Fig. 2 Isotherms of nitrogen adsorption and pore size distribu-
based on experimental experience, prevents formation of air tions of parent and modified ZSM-5 zeolite.
bubbles in the capillary tubes. At the beginning of the exper-
iment, the reference and measurement cells contained water
The influence of the alkaline treatment on the acidity of the
(1.5 cm3) and water with a weighted amount of the solid sam-
zeolite structure was investigated by coupled microcalorimetry
ple (ca. 50 mg), respectively. Initial solution concentrations of
and volumetry of ammonia adsorption. Fig. 4 presents the site
atenolol, diclofenac sodium and salicylic acid were the
strength distributions for the investigated samples. The results
same as in the previously described adsorption experiments.
show that the shapes of distributions are generally the same for
Hence, the calorimetric experiments were used to directly
both samples, consisting of two major domains, centered at
measure the heats which evolved due to adsorption (expressed
150 and 75–80 kJ mol1. Compared to the parent zeolite,
as J g1 of solid), for each admitted dose. Using previously
there is a slight decrease of the number of strong (150 kJ
determined corresponding adsorbed amounts, differential
mol1) and weak (75 kJ mol1) acid sites for the hierarchical
heats of adsorption (Qdif, expressed in kJ mol1) were
sample, while an increase of the number of sites with interme-
calculated.
diate strength (85–125 kJ mol1) is also noticeable. The
observed changes in the distribution of strength of the acid
3. Results and discussion sites are not drastic and it can be concluded that the acidity
of ZSM-5 remained unaffected to a large extent by the modi-
3.1. Characterization fication procedure. A detailed analysis of the obtained calori-
metric results is presented elsewhere (Rac et al., 2013).
The alterations of pore structure of zeolite ZSM-5, caused by The coordination state of Al in both zeolite samples was
the alkaline treatment, were investigated using low tempera- estimated by solid-state 27Al MAS NMR spectra (not pre-
ture nitrogen adsorption (Fig. 2). The modified sample shows sented here). The obtained results show that both the parent
a more than two-fold increase in the total amount of nitrogen and the modified sample predominantly contain tetrahedral
adsorbed compared to the parent zeolite. The isotherm of the Al (peak at 54 ppm), which is attributed to framework alu-
parent sample consists of an adsorption branch of type I and a minum. Some extraframework Al species, octahedrally coordi-
H4 type hysteresis, typical for microporous materials (Sing nated (peak at 0 ppm), were also found in the spectra of both
et al., 1985). The modified sample exhibits an isotherm of type samples. These results indicate that desilication did not result
IIb, with a steep slope at higher values of p/p0, and a H3 hys- in significant extraframework Al buildup. It is here important
teresis, which is in accordance with the results obtained by to point out that the total SiO2/Al2O3 ratio, measured by
other authors for hierarchical zeolites (Fernandez et al., chemical analysis, changed from 50 to 43 after the alkaline
2010; Wu et al., 2012). Alkaline treatment of ZSM-5 resulted treatment, but its value was restored to 50 again, after the sub-
in an increase of the total pore volume (from 0.236 to 0.449 sequent acid wash. This is in accordance with data obtained by
cm3 g1), mesopore volume (from 0.085 to 0.380 cm3 g1), Mitchell and Pérez-Ramı́rez (2011), who emphasized the
BET surface (from 365 to 470 m2 g1) and external surface importance of acid wash treatment, which removes non-
(65 to 173 m2 g1), which is attributed to mesopore formation framework aluminum resulting from alkaline treatment and
(Groen et al., 2004b). Microporosity of the zeolite was pre- recovers Si/Al composition similar to that of the starting
served to a high degree: only a slight decrease of the micropore material.
volume was measured (from 0.144 to 0.138 cm3 g1). The pore The point of zero charge (PZC) for both parent and meso-
size distribution of both samples is presented in Fig. 2 (inset). porous sample was determined by batch equilibrium method
The modified ZSM-5 sample exhibits a fairly broad peak cen- (Fig. 5). The obtained results show that the PZC value is
tered at 14 nm. Formed mesopores and differences in pore 2.95 ± 0.05 for parent and 3.05 ± 0.05 for mesoporous
structure between parent and modified zeolite are clearly visi- ZSM-5, indicating that the introduction of mesoporosity in
ble in TEM micrographs (Fig. 3). ZSM-5 did not lead to any significant change in surface charge.
Enhanced accessibility of active sites in hierarchical ZSM-5 zeolite 1949

Fig. 3 TEM micrographs of (a) microporous and (b) hierarchical ZSM-5.

Fig. 4 Distribution of strength of acid sites in parent and

modified ZSM-5 zeolite.

Fig. 5 pHf versus pHi for parent and modified ZSM-5 zeolite;
XRD patterns were recorded in order to estimate the influ-
PZC determination.
ence of desilication on the crystallinity of ZSM-5. The results
(not presented here) show that the diffraction patterns typical
for ZSM-5 structure were recorded for both samples and that behavior towards salicylic acid, atenolol and diclofenac. In
the desilicated sample preserved its crystalline structure. How- the case of salicylic acid there is a slight decrease of the overall
ever, the degree of crystallinity was altered in the modified zeo- adsorptive capability for the mesoporous sample, compared to
lite. The variation in crystallinity of the modified zeolite was the parent one (Fig. 6). However, this decrease is more pro-
calculated as proposed in literature (Martınez et al., 2013; nounced in the region of lower equilibrium concentrations
Auroux et al., 1996), from the intensities of the reflection at while maximal amounts of SA adsorbed on microporous and
23° 2h, taking the crystallinity of the parent sample to be hierarchical samples, calculated using Langmuir, Sips and
100%. The crystallinity of the mesoporous ZSM-5 was found Toth models are similar (Table 1). The best fit of the experi-
to be 76%. mental values was obtained using Toth equation and, in this
case, the extrapolated maximal adsorptive capacities for parent
and modified sample are almost the same, 0.00021 mol g1 and
3.2. Adsorption measurements and liquid phase 0.00022 mol g1, respectively. These results are in accordance
microcalorimetry with the fact that the molecular diameter of SA molecules,
4.6 Å (Kirumakki et al., 2003), enables them to enter into
Adsorption experiments revealed a distinct difference in the the micropores of ZSM-5. Consequently, no positive effect
way mesopore creation in ZSM-5 affected its adsorptive of mesopore existence in the structure on the adsorption
1950 V. Rac et al.

In the case of atenolol and diclofenac sodium adsorption,

the effect of mesopore formation is quite opposite: an increase
of the maximum adsorbed amount of both molecules is
observed for the alkaline treated sample compared to the par-
ent (Fig. 6). This effect is moderate for diclofenac sodium and
very pronounced for atenolol, where there is a more than
threefold increase of the maximal adsorbed amount. Obvi-
ously, the existence of mesopores in the desilicated sample
enables more of the adsorbate molecules to enter the zeolite
structure and interact with the active sites to a much larger
extent than in the case of the parent sample. The difference
in the enhancement of the adsorption capability towards
diclofenac and atenolol is probably caused by the structure
and shape of the molecules in question. The difference in
dimension between the two molecules (7
18.2 Å for ATL
(Fagerholm et al., 1999) and 3.5
8.3
7.0 Å for DFC (Xie
et al., 2012)) can also play an important role, considering the
zigzag channel structure of ZSM-5 zeolite. Since the acidity
of the zeolite was only mildly affected by the mesopore forma-
tion process and the surface charge remained unchanged, the
presumption that the geometry of the pores and molecules is
a crucial factor can be expressed.
Hence, the observed increases in adsorption capabilities
toward atenolol and diclofenac seem to be the result of the
availability of the adsorption sites to the adsorbing molecules,
which was the parameter that was actually changed by the
mesopore formation process. The molecules in the hierarchical
zeolite are able to bond to the adsorption sites which are inac-
cessible to them in the parent sample. The extent of the adsorp-
tion capability enhancement depends on the shape and the
diameter of both mesopores and the adsorbing molecules. Fit-
Fig. 6 Adsorption isotherms of salicylic acid, diclofenac sodium ting of the experimental isotherms to theoretical models
and atenolol. showed that the use of Toth equation resulted in best agree-
ment, for all adsorbent – adsorbate combinations (Table 1).
capacity for SA should be expected. In fact, our results However, in some cases, Sips and Langmuir models also ade-
indicate that bonding of salicylic acid to zeolitic inner surface quately fitted empirical data. It is, at this point, important to
is somewhat favored in narrow micropores. emphasize that good agreement between experimental values

Table 1 Isotherm parameters for adsorption of pharmaceuticals on parent and modified ZSM-5.
Microporous ZSM-5 Hierarchical ZSM5
SA DFC ATL SA DFC ATL
Fitted Freundlich equation
KF ((mol g1)(dm3 mol1)n) 0.00198 0.00330 0.00044 0.00519 0.00515 0.00166
n 0.33 0.31 0.21 0.50 0.34 0.24
R2 0.81121 0.85829 0.93729 0.91924 0.88849 0.87151
Fitted Langmuir equation
Sm (mol g1) 0.00025 0.00043 0.00001 0.00028 0.00052 0.00032
KL (dm3 mol1) 5080 10,242 23,276 1616 12,352 29,582
R2 0.95994 0.97496 0.96456 0.97776 0.98033 0.92088
Fitted Sips equation
Sm (mol g1) 0.00021 0.00039 0.00011 0.00023 0.00048 0.00035
KS (dm3 mol1) 6880 13,146 17,612 2336 13,590 20,960
n 1.63 1.47 0.69 1.28 1.22 0.74
R2 0.99651 0.98837 0.97010 0.97827 0.98177 0.91202
Fitted Toth equation
Sm (mol g1) 0.00021 0.00039 0.00011 0.00022 0.00051 0.00036
KT (dm3 mol1) 3801 8806 53,852 1525 9799 134,709
n 1.88 1.49 0.60 1.65 1.05 0.51
R2 0.99620 0.99152 0.97155 0.99477 0.99512 0.98589
Enhanced accessibility of active sites in hierarchical ZSM-5 zeolite 1951
 
and a given model is very useful for interpretation and analysis c0  ceq 1
of the results, but should not be used as definite proof of the 100 ¼ 1  100 ð7Þ
c0 1 þ k mV
theoretical postulates the model is based upon (Adamson,
1990). Nevertheless, further analysis of the results obtained c c
where 0 c0 eq 100 (%) is the relative decrease of adsorbate con-
using Toth equation allowed us to easily evaluate and compare centration due to adsorption, i.e. the efficiency of the process
adsorptive capabilities of the investigated zeolites at low con- and k = SmKT. Eq. (7) can be used to calculate V and m values
centrations. Toth equation reduces to linear shape in the which are needed in order to obtain a desired adsorption effi-
region of low concentrations. Indeed, this is a property that ciency or to compare efficiencies of different adsorbents for
adequately depicts the real situation: when the concentration given V and m. Fig. 7 presents atenolol removal efficiencies
of the adsorbate is very small, the available concentration of for the investigated microporous and hierarchical ZSM-5 sam-
adsorption sites within the zeolite is, relatively, so large that ples, for different m/V values. The results show that enhanced
it can be regarded as ‘‘infinite” in the sense that its change dur- adsorptive capability of modified ZSM-5 becomes more pro-
ing the adsorption process is negligible. Hence, at these condi- nounced with decreasing m/V ratio.
tions, the adsorbed amount becomes solely dependent of the To further investigate the interaction between the active
adsorbate concentration and the isotherm is theoretically sites of the zeolite samples and the adsorbing molecules, liquid
expected to be linear. Toth equation becomes linear when KT- calorimetry measurements were conducted. For each of the
ceq  1, which reduces Eq (4) to molecules, calorimetric experiments were performed in the
concentration range corresponding to the part of the isotherm
Se ¼ Sm KT ceq ð5Þ
before the saturation plateau, where the strongest binding is
Using Eq (5) and data in Table 1, it can be shown that, for a expected. In the case of atenolol adsorption, a remarkable
given ceq, Se of hierarchical sample is approximately 8 times increase of the strength of interaction was detected for the hier-
larger than Se of microporous sample, in the case of atenolol archical sample compared to the parent zeolite (Fig. 8). The
adsorption. Hence, superior adsorptive capabilities of modified heats of adsorption in the initial regions of the two calorimet-
ZSM-5 towards atenolol are expected to be even more pro- ric curves show almost a 30 kJ mol1 difference. Considering
nounced in low concentration situations. the previously described distribution of strength of the active
Aside from Eq (5), which is specific for a given adsorbate – sites of the two zeolite samples, this increase of the atenolol
adsorbent couple, another mathematical relation between – hierarchical ZSM-5 interactions can be interpreted as a result
adsorbed amount (Se) and equilibrium concentration (ceq) of enhanced accessibility of strong adsorption sites within the
exists: zeolite structure to atenolol molecules. However, this increase
is limited to the initial region of the calorimetric curve after
V which the strength of the interaction becomes equal to that
Se ¼ ðc0  ceq Þ ð6Þ detected for the parent sample. It seems that, in the case of par-
m
ent microporous sample, atenolol can be adsorbed only at its
where V is the total volume of the solution, m is the mass of surface; since the dimensions of its molecules prevent them
zeolite used and c0 is the initial concentration of the adsorbate. from entering three-dimensional interconnected channel sys-
This equation gives all possible pairs of Se and ceq values which tem of ZSM-5 zeolite. Evidently, the formation of mesopores
are theoretically possible for given V, m and c0. Combining enabled ATL molecules to reach adsorption sites stronger than
Eqs. (5) and (6) yields: those existing at the surface of zeolite.
For the two other investigated molecules, such a drastic
change in the strength of interactions with the zeolite samples
(microporous and hierarchical) was not detected. The mea-
sured heats of adsorption for diclofenac sodium were approx-
imately 45 kJ mol1. The calorimetric effects for salicylic acid
adsorption were below detection limit, since in this case, we
did not obtain signals which differed significantly from the
baseline of the calorimeter. Generally, the existence of basic
or acidic groups in the adsorbing molecules determines their
strength of interaction with ZSM-5. Evidently, the interactions
between zeolitic acid sites and basic groups of atenolol mole-
cules result in the strongest bonds. The values of differential
heats of DFC adsorption indicate somewhat weaker interac-
tion with ZSM-5 structure, which is in agreement with weakly
basic character of the molecule. In the case of salicylic acid, it
is reasonable to assume that its acidity (pKa = 2.97) prevents
strong adsorption. Obviously, salicylic acid interacts with
ZSM-5 structure forming very weak bonds so the heats of
adsorption could not be detected.
It has to be underlined here that the charge of an adsorbate
in a solution (i.e. weather the molecules are dissociated, proto-
nated or not) as well as the surface charge of the adsorbent are
Fig. 7 Removal efficiencies for atenolol at low initial concen-
expected to be important factors in adsorption processes.
trations for different m/V.
1952 V. Rac et al.

on ZSM-5 surface toward specific pharmaceutical molecules

and (2) dimensions of both the adsorbing molecules and the
pore structure of the zeolite. The results presented here give
evidence about the importance of steric effects: among the
probed pharmaceuticals, atenolol and diclofenac were more
effectively adsorbed on mesoporous then on microporous zeo-
lite. It was shown that, in the case of atenolol, superior adsorp-
tive capabilities of hierarchical ZSM-5 can be expected to be
even more pronounced at low initial concentrations. Hence,
it is to be underlined that forming of mesopores can signifi-
cantly improve the accessibility of active sites inside the
ZSM-5 structure. In view of the fact that microporosity of zeo-
lites presents their major drawback for their application as
adsorbents in the domain of environmental protection and
remediation, results presented in this work clearly show that
the applicability of these materials can be improved by meso-
pore formation.

Acknowledgments

Fig. 8 Differential heats of adsorption of atenolol obtained by Serbian Ministry of Education and Science (Project 172018) is
liquid calorimetry. acknowledged for financial support.

However, although the state of a molecule in a solution is

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