Microporous and Mesoporous Materials 232 (2016) 174e183

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Microporous and Mesoporous Materials

journal h om epage : www. e l s e v ie r .c o m /l o c a te / m i cr om e s o

Synthesis and characterization of zeolite based nanoecomposite: An

environment friendly slow release fertilizer
Ambreen Lateef a, Rabia Nazir b, *, Nadia Jamil a, Shahzad Alam c, Raza Shah d,
Muhammad Naeem Khan b, Murtaza Saleem e
a
College of Earth and Environmental Sciences, University of the Punjab, Lahore 54500, Pakistan
b
Applied Chemistry Research Centre, Pakistan Council of Scientific and Industrial Research Laboratories Complex, Ferozepur Road, Lahore 54000, Pakistan
c
Pakistan Council of Scientific and Industrial Research Laboratories Complex, G-5/2 Islamabad, Pakistan
d
H.E.J Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
e
Department of Physics, School of Science and Engineering, Lahore University of Management Sciences, Lahore 54792, Pakistan

articleinfo abstract

Article history: The research deals with assessing the feasibility of using nano-zeolite as support material for the pro-
Received 5 March 2016 vision of nine out of thirteen primary, secondary and micro-nutrients on slow release basis. The nano-
Received in revised form zeolite (NZ) and nano-composite (ZNC), synthesized using simple chemical approach, were character-
8 May 2016 ized by different techniques including FT-IR, powder XRD, SEM/EDX, AFM and TGA/DSC. Physical char-
Accepted 12 June 2016 acterization was also performed by using standard methods. The lab studies showed that there is
Available online 14 June 2016 considerable increase in water retention capacity, water absorbency, equilibrium water content and
swelling ratio of ZNC as compared to the NZ which is favorable for maintaining water level in the soil. The
Keywords: nano-composite prepared is safe to use as compared to conventional fertilizers as indicated by salt index
Nano-zeolite value. Nutrients slow release studies carried out in water and soil con firmed the long term availability of
Zeolite based nano-composite
all the doped nutrients to the plant over the full crop cultivation period that is suitable for p romoting
Slow release fertilizer
germination, growth, flowering and fruiting. Hence, the results obtained showed that the prepared nano-
Macro and micro-nutrients
composite materials can be safely used as environment friendly fertilizer.
© 2016 Elsevier Inc. All rights reserved.

1. Introduction
Agriculture practices are very important for people all over the
world for providing food but unfortunately these methods are facing
several international challenges now days. One such chal-
lenge is massive increase in the population which had put enor-
mous burden on the agronomic productions that need to be
enhanced with same limited resources of land and water. This
resulted in significant rise in fertilizers’ usage to enhance soil health
Abbreviations: AFM, Atomic Force Microscopy; DSC, Differential Scanning
Calorimetry; EDX, Energy-dispersive X-ray Spectroscopy; EWC, Equilibrium Water
Content; FTIR, Fourier Transforms Infrared Spectroscopy; HDTMA, Hexa Decyl Tri-
methyl Ammonium; SI, Salt Index; SR, Swelling Ratio; SRF, Slow Release Fertilizer;
SEM, Scanning Electron Microscope; SMZ, Surface Modified Zeolite; TGA, Thermal
Gravimetric Analysis; TDS, Total Dissolved Solids; TH, Total Hardness; WR, Water
Retention; WA, Water Absorbance; XRD, X-ray Diffraction; ZNC, Zeolite Based
Nano-composite.
* Corresponding author.
E-mail address: rabiapcsir@yahoo.com (R. Nazir).
that can expedite fast increase in yield per hectare [1]. However,
this uncontrolled use of fertilizers had not only caused decline in
land quality but owing to their high solubility which results in
40e75% leaching losses, they contribute less towards plant growth
and more towards environmental issues [1e3] which directly or
indirectly lead to various health concerns [4]. Furthermore, this
incurs in huge wastage of fertilizers accounting for economic loses.
All these issues together can put enormous financial burden on the
society which is not only a matter of serious concern for developing
countries which are striving for survival but also for developed
countries in attaining sustainability. Therefore, there is a dire need
to change agronomic practices by designing new environmental
friendly fertilizers that can also enhance crop yield by facilitating
maximum nutrient uptake.
Application of nanotechnology in this area can help in pro-
moting sustainable agriculture by provision of slow or controlled
release fertilizers, herbicides and pesticides [5e7]. Several re-
searches have been carried out in this context which dealt with the
development of nanoparticles or nano-composites to facilitate

http://dx.doi.org/10.1016/j.micromeso.2016.06.020
1387-1811/© 2016 Elsevier Inc. All rights reserved.
 A. Lateef et al. / Microporous and Mesoporous Materials 232 (2016) 174e183
plant growth either by direct uptake or by slow release of nutrients
[8]. Total of 16 nutrients are required by the plants out of which 13
are usually taken up from the soil. Nano-fertilizers have helped in
provision of these essential nutrients to the soil on continues basis by
slow release. This gradual release promotes enhanced delivery of
nutrients to the plants that further accelerates early germination, fast
growth and high nutritional level [9].
Zeolite, in general, is known to support crop cultivation by
improving soil condition through enhancing nutrients and water
utilization efficacy, biological activity and fertility and minimizing
ammonia volatilization and soil salinity [10e14]. Additional
advantage of zeolite is that it enhances the nutrient retention ca-
pacity of soil which leads to increased availability of nutrients to the
plants for longer period of time because of its slow disintegration
and decomposition rate in soil [5]. Considering all these advantages
of zeolite, the material has recently gained much attention and is
being used to deliver fertilizer to the plants at slow rate after some
structural modifications [15e19]. Not much of the work is cited on
applicability of nano-zeolite as slow-release fertilizer, the few
studies that have been carried out are conducted by Subramanian
et al. [20,21]. They showed that these nano-zeolites release nutri-
ents over a much longer period of time when compared with
conventional fertilizers thereby reducing nutrients’ leaching losses
considerably [22]. High pore density, enhanced surface area and
anion exchange capacity of nano-zeolites favors the retention of
anions [20,23,24].
The only drawback associated with the use of these fertilizers is
related with their incapability in loading cations in considerable
amounts on to its porous structure. For this purpose various
structural modifications were performed to increase both cation and
anion uptake capacities either by use of surfactants [21,22] or by
prolonged thermal treatment [20]. These additional treatments
not only add up to the cost of fertilizers but also the use of sur-
factants put extra burden on the environment [25,26].
Therefore, the need is to design simple and cost-effective ways
for the synthesis of nano-zeolite that can enhance the nutrient uptake
capacity in addition to reducing the environmental impacts caused
by use of conventional and environmental hazardous ma- terials.
The current research is henceforth aimed to develop simple
methodology for synthesis of nano-composite of zeolite that not only
facilitates the enhancement in ion exchange capacity but also acts as
a material that can act as a continues source of both macro and
micro-nutrients throughout the period of crop growth.
2. Experimental
2.1. Chemicals
All chemicals used in the study are of analytical grade. Sodium
phosphate monobasic dihydrate (NaH 2PO4$2H2O), magnesium
sulphate heptahydrate (MgSO 4$7H2O), aluminum sulphate hepta-
hydrate (Al2(SO4)3$7H2O), and ethylene glycol (C 2H6O2) were taken
from Merck, Germany. Sodium hydroxide (NaOH), calcium phos-
phate (Ca3(PO4)2), zinc sulphate heptahydrate (ZnSO 4$7H2O) po-
tassium chloride (KCl) and sodium silicate solution (Na 2SiO3) were
procured from DAEJUNG while sodium chloride (NaCl), sodium
nitrate (NaNO3), ferrous chloride tetrahydrate (FeCl 2$4H2O), nitric
acid (HNO 3) and hydrochloric acid (HCl) were supplied by Sigma-
Aldrich.
2.2. Synthesis of zeolite nano-composite (ZNC)
Two-step approach was adopted to synthesize ZNC; in first step
zeolite was prepared that was impregnated with nutrients in sec-
ond step.
175
2.2.1. Synthesis of nano-zeolite (NZ)
Nano-zeolite (NZ) was synthesized by simple co-precipitation
method [27]. Sodium silicate solution (220 g/300 ml distilled wa-
ter) and ethylene glycol (25 ml) were taken in a three necked round
bottom flask fitted with reflux condenser and quick fit dropping
funnels. The contents were stirred for 30 min while maintaining the
temperature at 50e60 ○C to get homogenous mixture. To this
aluminum sulphate (78.7 g/250 ml) and sodium hydroxide (30 g/
250 ml) solutions were added drop-wise along with stirring and
heating (50e60 ○C). When dropping was completed pH was
adjusted to neutral using 1 N HCl followed by filtration, oven drying
at 105 ○ C and annealing at 650 ○ C to result in grey colored zeolite.
2.2.2. Synthesis of zeolite nano-composite (ZNC)
The zeolite based nano-composite (ZNC) was synthesized by
simple impregnation of nutrients in NZ. To the suspension of NZ in
distilled water (200 g/l) 5% solution of each of macro (N, P, K, Ca, Mg,
S) and micro-nutrients (Fe, Zn, Cu) in the form of their salts
(NaH2PO4$2H2O, MgSO4$7H2O, Ca3(PO4)2, ZnSO4$7H2O, KCl, NaNO3
and FeCl2$4H2O) were added and allowed to stir for 3 h to attain
maximum impregnation of these nutrients into NZ. The resulting
suspension was vacuum filtered, oven dried (105 ○
C) and fine
grinded in blender at 12,000 rpm. The prepared zeolite was stored
in air-tight container till further use.
2.3. Characterization
2.3.1. Physical properties
The physical properties including pH (ASTM D 4959-00), con-
ductivity (ASTM D1125-14), moisture content (ASTM 4643-08), bulk
and tap densities (ASTM D2854-70), methylene blue (MB) value
(ASTM C1777-15), ash content (ASTM D2866-70) and cation
exchange (CEC) and anion exchange (AEC) capacities of NZ and ZNC
were determined by standard methods [28].
2.3.2. Fourier transform infrared spectroscopy (FT-IR)
The material FT-IR Thermo Nicolet spectrometer series by
scanning the sample pallet made with KBr in the range of 4000e400
cm—1.
2.3.3. Powder X-ray diffraction (XRD)
Powder XRD analysis was carried out using PANanalytical X’pert
pro diffractometer by a Philips X-ray generator. Diffraction data was
acquired by exposing powder samples to Cu-Ka X-rays radiation,
which has a characteristics wavelength of 1.5418 A ○. X-rays were
generated from a Cu anode supplied with voltage of 40 kV and a
current of 40 mA. The data were collected over a range of 20e80○2q
with a step size of 0.05 and nominal time per step is 0.5 s.
2.3.4. Scanning electron microscopy (SEM) and energy dispersive x-
ray spectroscopy (EDX)
Gold coated pallets of the samples were used to acquire the SEM
images on Nova NanoSEM 450 while powder samples spread on
carbon tape were used to determine the elemental composition
using EDX, Nova 450 at 5.00 kV.
2.3.5. Atomic force microscopy (AFM)
The topographic images of atomic force microscopy were
recorded with AFM 5500 (Agilant, USA). Silicon nitride probe with a
triangle soft cantilever (Veeco, model MLTC-AUHM) having a
nominal value of the spring constant of 0.01 and 0.1 N/m used in the
non-contact topography measurements. Ethanolic solution of
sample (100 mg/ml) was vortexed for 1 min followed by sonication
(KQ 500-DE) for 30 min. From this 10 ml solution was taken and
176 A. Lateef et al. / Microporous and Mesoporous Materials 232 (2016) 174e183

deposited on a freshly cleaved mica surface to obtain images using 2.8. Slow release studies
AM in tapping mode.
Two types of slow release studies were conducted for ZNC to
determine the nutrient leaching pattern in 1) water and 2) soil.
2.3.6. Thermal gravimetric analysis
Thermo gravimetric analysis (TGA and DSC) was carried out 2.8.1. Slow release studies in water
using a SDT-Q600 (Germany) instrument; 3 mg of sample was taken Seven days slow release or leaching pattern of ZNC in water was
in an alumina cup and scan was recorded at heating rate of 20 determined by conducting experiment in glass column (3000 × 0.500 )
○C/min over the range of 50e1000 ○C to find the thermal sta- bility
using 5.0 g of ZNC and pre-analyzed tap water (Table 1). The volume
of material. of water was maintained at 50 ml mark throughout the experiment.
During the seven days period, water in increments of 25 ml was
2.4. Salt index (SI) collected daily at 24 h time interval to determine the leakage of
nutrients within span of 7 days [32].
1.0 g each of ZNC and sodium nitrate were taken in separate
beakers and200 ml of distilled water was added in each of the 2.8.2. Slow release studies in soil
beaker. After 24 h, the conductivities of solutions were taken using 14 days column studies were done by employing glass column
(6200 × 500 ) filled with 400 g of sieved soil mixed thoroughly with
10 g of ZNC.180 ml pre-analyzed tap water (Table 1) was added to
conductivity meter CM-40S TOA and SI was calculated as ratio of
these conductivities [29].
the column to saturate the soil. 50 ml water was collected daily at
24 h interval from the column for the period of study. 100 ml water
2.5. Swelling ratio (SR) and equilibrium water content (EWC) was then added to ensure constant moisture content in the column.
The collected water samples were analyzed to check the release
1.0 g of ZNC and NZ was immersed in distilled water (200 ml) pattern of nutrients from nano-composite in soil. The experimental
and allowed to swell for 24 h under ambient conditions of tem- blank using just soil sample (400 g) was run under same set of
perature and pressure. The contents were filtered and SR and EWC conditions [33].
were calculated using Eqs. (1) and (2), respectively [29]. The collected samples (from above experiments) were analyzed
for metals (Zn2þ , Fe2 þ/3þ, Ca2þ , Mg2þ ) by Perkin E lmer Flame
Ws — Wd Atomic Absorption Spectrometer (FAAS), ( Na1þ, K1þ ) by Flame
SR ¼ (1)
Wd Photometer Tenway PSP7, Holand, NO 1— 3 by Ion Selective Electrode
930 and PO 3
—
4 by UV Visible Spectrophotometer.
Ws — Wd
EWCð%Þ ¼ × 100 (2)
Ws 2.9. Statistical analysis
where, WS and Wd are the wet and dry weights of ZNC or NZ,
The data was analyzed using Microsoft Excel and OriginPro 8.5
respectively.
software. All the readings are reported as average of three. For slow
release studies the readings for blank are adjusted prior to simu-
2.6. Water absorbance (WA) studies lation of results in order to get the true picture of nutrients released
only from ZNC.
These studies were carried out by taking 1.0 g of NZ and ZNC
(W1) in pre-weighted petri-dishes (W2). These petri-dishes were 3. Results and discussion
kept in desiccator under moist environment for 5 days and re-
weighted (W3) to check the sample water absorption capacity This research defines a simple method to synthesize ZNC using
(WC) by using Eq. (3) [30]. impregnation approach to load both macro (primary and second-
ary) and micro nutrients onto NZ in the ratio of 5%. The synthesized
ðW3 — × 100 (3) materials (both NZ and ZNC) were characterized using FT-IR, SEM/
WC ¼
W 2Þ EDX, AFM, powder XRD, TGA and DSC to get insight into their
W1 structure, morphology, chemical composition, particle size and
thermal stability. Physical characterization was also performed
using standard methods. To find the applicability of the ZNC as slow
2.7. Water retention (WR) studies
Table 1
Water retention capacity (WR) was measured using pre- Water analysis.
weighted cups A (WA) and B (WB) with sieved bottom. 50.0 g sieved
Parameters Results
soil from field was taken in cup A and in cup B 2.0 g of ZNC was
taken after mixing with 50 g soil followed by addition of 30 ml pH 7.8
distilled in each cup. Water was allowed to seep through them and Conductivity ( ms/cm) at 25 ○ C 290.50
TDS (mg/l) 413.3
cups were reweighed (WA1 and WB1) after 24 h. The cups were then
TH (mg/l) 0.7
kept in a glass box and weighted (WA2 and WB2) daily for next 30 days Ca2þ(mg/l) 0.36
allowing 24 h interval between the readings [31]. The following Mg2þ (mg/l) 0.34
equation (Eq. (4)) was used to calculate water retention. Zn2þ (mg/l) 0.04
Cl1— (mg/l) 17.75
W2 Na1þ (mg/l) 2.1
WR ¼ × 100 (4) K1þ (mg/l) 1.0
W1 PO43— (mg/l) 2.4
NO31— (mg/l) 0.9
 A. Lateef et al. / Microporous and Mesoporous Materials 232 (2016) 174e183 177

Table 2 release fertilizer, related studies like SI, SR, EWC, WA, WR and
Physical parameters of NZ and ZNC. nutrient slow release studies were also performed.
Parameters NZ ZNC

pH 6.97 6.0
3.1. Synthesis of ZNC
Moisture content (%) 2.5 4.48
Conductivity (ms/cm) at 25 ○ C 508.27 555.23 Simple co-precipitation method was used to prepare NZ which
Bulk density (mg/m3) 0.89 1.2 was further used to synthesize ZNC by simple impregnation of
Tap density (mg/m3) 1.5 1.8
macro- and micro- nutrients. Zeolite in general has a porous
Cation exchange capacity (meq/g) 2.45 1.37
MB value 60 65 structure [34] and use of templating agent further promotes in-
Ash content (%) 91.37 94.27 crease in porosity and surface area. Hence, when impregnation is
done nutrients penetrate into the pores and from one pore to

Fig. 1. FT-IR spectra of NZ (A) and ZNC (B) showing peak shifting in ZNC due to doping.
 178 A. Lateef et al. / Microporous and Mesoporous Materials 232 (2016) 174e183
another pore, ensuring more adsorption of nutrients and therefore
enhanced availability to the plants. These nutrients will be released
from ZNC depending upon the pore size, adsorption level, and
binding capacity or impregnation level [35].
3.2. Characterization
3.2.1. Physical parameters
Experiments were performed to determine physical parameters
i.e. pH, moisture, conductivity, bulk density, tap density, CEC, AEC,
MB value, loss on ignition and ash content for both NZ and ZNC. The
results obtained are tabulated in Table 2.
NZ is a neutral material as observed from its pH value, but there is
a small increase in acidity of ZNC probably due to incorporation of
non-metallic moieties. Significant increase in conductivity of ZNC
from 508.27 to 555.23 mS/cm has taken place owing to inclusion of
20 30 40 50 60 70


Fig. 2. Powder XRD of NZ (A) and ZNC (B) showing amorphous nature of samples.
Fig. 3. SEM images of NZ and ZNC at resolution of 10 mm (A & B) and at 1 mm (C & D), respectively.
metals and ionic salts into zeolite porous structure. This incorpora-
tion of salts has also resulted in increase in both tap and bulk den-
sities. Very high moisture content is indicated by the studies which is
accordance with the previous studies that state that nano-zeolites
with high Si/Al ratio are usually characterized with high moisture
content because of enhance hydrophobicity induced by silica [28].
The lower MB value is recorded in case of ZNC (60) as compared
to NZ (65) because of impregnation of metals into the NZ structure.
The NZ has cation exchange capacity (CEC) of 2.45 meq/g which is
comparable with the clinoptilolite [28] and anion exchange ca- pacity
is 0.01 meq/g which is very low; while ZNC has cation and anion
exchange capacities of 1.37 and 1.96 meq/g. The decrease is observed
in CEC of ZNC as compared to NZ owing to incorporation of cations
into NZ matrix. Low anion exchange capacity is observed in case of
NZ making it specifically cation exchanger [36]. But for ZNC equally
good AEC is observed hence it can be claimed as amphoteric ion
exchanger [37] which makes it better material for agricultural
purposes [38].
3.2.2. Fourier transform infrared spectroscopy (FT-IR)
Fig. 1 gives the comparison of FT-IR spectra of NZ and ZNC. The
peaks in the range of 3400e3200 cm—1 are due to extra bridging of
hydroxyl ion or due to moisture incorporated in the porous struc-
ture of zeolite as affirmed from physical characterization as well. The
peaks arising at 1060.85 and 786.96 cm —1 are assigned to bending and
stretching of AleO and SieO in zeolite structure [39]. The peak
shifting is in FI-TR spectra of ZNC to 3034.03, 1070.49, 796.60, 594.06,
557.43 and 507.28 positions which may be attrib- uted to
incorporation of nutrients in the zeolite structure hence, supporting
the doping of nutrients on the NZ as available in the literature [40].
80 3.2.3. Powder x-ray diffraction (XRD)
Powder XRD patterns of NZ and ZNC scanned in range of 2q
¼ 20e80○ are shown in Fig. 2. The low crystalline structure of NZ
 A. Lateef et al. / Microporous and Mesoporous Materials 232 (2016) 174e183 179

Fig. 4. EDX analysis of (A) NZ and (B) and ZNC showing composition of elements in table inset.

spectrum is matched with sodium aluminum silicate having cubic

crystal system and CCDC No: 01-074-1183. The ZNC spectra (Fig. 2B)
when compared with NZ represents that basic structure of zeolite is
not changed just a slight decline in the intensities resulted which is
due to incorporation of nutrients into NZ [41]. The presence of low
intensity broadened peaks is also indicative of small particle size of
the samples prepared [42,43].

3.2.4. Scanning electron microscopy (SEM)/energy dispersive x-ray

spectroscopy (EDX) and atomic force spectroscopy (AFM)
After structural characterization, SEM analysis was conducted to
get insight into the morphology of the samples prepared. The mi-
crographs of NZ and ZNC (Fig. 3A and B) corresponds to the spongy
nature of prepared samples. Increase in the particle size, reduction
in porosity and appearance of white colored coating on the particles
in case of ZNC spongy appearance shows doping effect.
Compositional analysis of elements was done by EDX which is
presented in Fig. 4. The chemical formula derived from this
composition (Fig. 4 inset table) by fitting in the values in general
formula of zeolite (i.e. [AlxSiyO2xþ2y]x— where x ≤ y) points to the
formation of high silicon zeolite i.e. [AlSi 6O12].Na2. The charge (x —)
is stabled by incorporation of an added cation (Na1þ, K1þ, Ca2þ, etc) as
mentioned in the literature [44,45]. The Si/Al ratio hence ob- tained
is 6.15 for the NZ and 10.7 for ZNC (Fig. 4 inset Table) which also
points towards the incorporation of other metallic and non- metallic
impurities and amount of Si or Al exchanged [46]. This study is also
in accordance with ion exchange capacity studies discussed earlier.
Particle size of ZNC was determined using AFM by taking both
2D and 3D images as presented in Fig. 5. The 2D image (Fig. 5A)
depicts the narrow distribution of particles in size range of 3e6 nm
with majority of particles having size of 6.05 nm as confirmed from
3D image (Fig. 5B). The increase in particle size as affirmed from
SEM (Fig. 3) and AFM (Fig. 5) images is also attributed to high Si/Al
Fig. 5. AFM images in (A) 2D and (B) 3D of ZNC showing particle size in range of ratio in ZNC [47].
3e6 nm.

3.2.5. Thermogravimetric analysis

is indicated (Fig. 2A) with low intensity peaks arising at 2q values of To determine the stability and thermal degradation pattern of
23.32○, 25.82○, 28.89○, 31.59○ and 33.85○ corresponding to (311), samples prepared, TGA and DSC analysis were conducted which are
(222), (400), (311) and (421) hkl diffraction planes, respectively. The
180 A. Lateef et al. / Microporous and Mesoporous Materials 232 (2016) 174e183

Fig. 6. TGA (black line) and DSC (blue line) spectra of NZ showing minor weight loss. (For interpretation of the references t o color in this figure legend, the reader is referred to the
web version of this article.)

given in Figs. 6 and 7 as interlinked spectra. The TGA of NZ (Fig. 6)
thermogram is characterized by one single slope with continuous
but smooth weight loss which is typical of the spectra recorded for
zeolites [28,48]. The initial weight loss occurring around 100 ○C is
attributed to loss of water physically adsorbed which approximately
accounts for wt. loss of 2.5% that is line with the moisture obtained
in physical characterization studies (Table 1). This is followed by
further incremental decrease up to 500 ○C associated with loss of
matrix bound water [28]. The total weight loss is approximately
8.9%. As temperature raises, breakdown of hydroxyl ion increases
but in overall the de-hydroxylation process of zeolite is slow and
occurs in temperature range of 500e800 ○C [45]. The weight loss of
NZ occurred till 981.86 ○C accounting for 85.32% residue.
The different Si/Al ratio of zeolite were found responsible for the
thermal stability of zeolite; in general the zeolites with ratio up to 6
shows more stability than zeolites with lower ratio [46]. This trend
of NZ thermal degradation when compared with ZNC thermogram
(Fig. 7) is observed to be nearly same except that small incremental
steps can be seen owing to dehydration resulting from weight loss
of physically bound water (124.97 ○C; Wt. loss 4.56%), matrix bound

Fig. 7. TGA (black line) and DSC (blue line) spectra of ZNC showing incremental weight loss. (For interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article.)
 A. Lateef et al. / Microporous and Mesoporous Materials 232 (2016) 174e183 181
WR of Soil
WR of Soil+ZNC water (482.16 ○C; Wt. loss 6.38%) and oxidation of metallic species
100 accompanied by decomposition of nitrates, sulphates and phos-
phates resulting in evolution of gaseous moieties (Residue 82.07% at
919.62 ○C) [49]. This kind of almost linear behavior is consistent with
80 earlier studies [45]. Overall both the samples showed high stability.
The results of residue obtained in both the cases are in accordance
with loss on ignition and ash content studies performed earlier.
60 DSC curves of NZ and ZNC are given in Figs. 6 and 7 which are
characterized by having dehydroxlation endotherms in range of
WR (%)

50e600 ○ C with first low temperature peaks appearing around 100

○C in both samples and other shallow peak appeared with minima
40
at 596.30 ○C corresponding to △H 87.83 J/g for ¼ NZ. In case of ZNC
another high temperature board endothermic peak with minima at
20 920 ○C with high △H 825.21 J/g value which ¼ probably accounts for
decomposition of non-metallic moieties.

0 3.3. Salt index (SI)

0 5 10 15 20 25 30
No. of Days SI is also calculated to assess the probable potential of prepared
fertilizer to cause plant injury; higher the potential larger the
Fig. 8. Water retention capacity of soil without ZNC and with ZNC.

Fig. 9. Slow release pattern of percentage release of nutrients (NO1 —, P O , K O, Na O, Fe2þ/3 þ, Zn2 þ, Ca2þ and Mg2þ) in tap water for seven days studies.
3 2 5 2 2
182 A. Lateef et al. / Microporous and Mesoporous Materials 232 (2016) 174e183

damage caused to plant leading to less crop yield. The acceptable
range for SI is terms of electrical conductivity should be less than 2
mmhos/cc which in case for ZNC comes around 0.5 mmhos/cc [50].
The SI expressed in terms of ratio to NaNO 3 (taken as 100),
conductivity comes out to be very low for both the NZ and ZNC,
when compared with urea which has very high SI value. The low
value shows that the prepared fertilizer is safe for plant use and is
also suitable for the seed row placement in agriculture, hence can
result in high yield crops as well [51].
3.4. Water absorbance (WA), swelling ratio (SR) and equilibrium
water content (EWC)
WA [52], SR [53], EWC [29] are essential features for the SRF. The
results of experiment for NZ and ZNC for all these three parameters
are 49, 63%; 3.28, 3.53 g/g and 76.63, 77.92%, respectively. Small
increase in all the three parameters was observed in case of ZNC as
compared to NZ. Zeolite, in general, has high porosity due to which
it can hold water more than half of its weight. Water can penetrate
into porous structure of ZNC and provides moisture to plants in dry
areas to improve yield [44]. In addition to that presence of water also
enhances the slow release of nutrients to the crops [52].
3.5. Water retention (WR)
WR, another significant property for SRF, is essential for agri-
culture in arid and desert areas for saving water to improve plants’
health [54]. Fig. 8 presents water holding capacity of ZNC mixed
with soil and soil without ZNC as control. The soil mixed with ZNC
has water retention capacity of 94.04 and 69.14% on 3rd and 20th day
while soil without ZNC has 75.01 and 55.5%, respectively. The rate
of water retained in case of soil alone is approx. 18% less than that of
soil ZNC indicating
þ ZNC has higher water holding capacity which
is in accordance with the absorbency studies. This retained water
helps in enhancing water availability, making it available to soil and
consequently to plants as per requirement [11].
3.6. Slow release studies
These studies were conducted both in tap water (Fig. 9) and in
soil (Fig. 10) separately to check the impact of these two on the slow
release pattern. In both the cases, the studies were conducted in
triplicates and the data is presented as average of percentage of
nutrient released out of total available nutrients present in ZNC
(Fig. 4). The results hence obtained helps in getting know-how

PO KO 2+
2 5
Zn
2

0.7 0.20 0.10 0.05

0.19

0.18 0.09
0.6
0.17

0.16 0.04
0.08
0.15
0.5
0.14
0.07
0.13
Amount released (%)

0.03
0.4 0.12
0.06
0.11

0.10
0.05
0.3 0.09
0.02
0.08
0.04
0.07
0.2
0.06
0.03
0.05
0.01
0.04
0.1
0.03 0.02

0.02

0.01 0.01
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16

No. of Days No. of Days No. of Days No. of Days

15 0.040

0.6
50
0.035

0.5
40 0.030

10
0.4
0.025
Amount released (%)

30

0.3
0.020

20

0.015 0.2
5

10
0.010
0.1
 A. Lateef et al. / Microporous and Mesoporous Materials 232 (2016) 174e183 183
0.005
0
0.0

0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16

No. of Days No. of Days No. of Days No. of Days

Fig. 10. Slow release pattern of percentage release of nutrients (NO 1—, P O , K O, Na O, Fe2þ/3þ, Zn2þ, Ca2þ and Mg2þ) in soil for 14 days studies.
3 2 5 2 2
184 A. Lateef et al. / Microporous and Mesoporous Materials 232 (2016) 174e183
about the exact release of specific nutrients present in the fertilizer
and also their availability to the plant on daily basis. These kind of
studies are an acceptable approach for selecting the suitability of
fertilizer to a crop as reported in literature [18,55]. 7-day release
studies performed in pre-analyzed tap water (Table 1) shows a set
pattern for release of nutrients i.e. NO 1—3, P O 2 , 5K O,
2 Na O,
2 Fe
2þ/3þ
and Mg 2þ (Fig. 9) i.e. initially the release is little faster which de-
[9]
creases with the time period except for magnesium and nitrate. In
case of magnesium gradual decrease in percentage of release was
observed with increase in time while for nitrate the incremental
increase with increase in time is noticed.
14 days nutrient release studies carried out in case of soil (Fig.
10) exhibited the same trend as was observed in case of tap water
except that the concentration of nutrients released is little higher
than that in water. The results obtained are well in accor- dance
with previous studies carried out and the trend observed favors
continues supply of nutrients to plants thereby preventing
leaching loses that are commonly observed with tradition fertil-
izers [55]. In addition to that availability of high nutrient content in
start also supports early seed sprouting and germination of plant
which facilitates the growth of healthy plant. After the initial high
dose to the plant, continues release supplied by ZNC helps in early
flowering and fruiting leading to high yield crops. The release of
nutrients from the fertilizer having porous structure depends upon
the pore size and difference in chemical composition of nutrients
[35].
4. Conclusion
The study is based on synthesis on zeolite based nano- composite
material as a potential environmental friendly slow- release fertilizer
having average particle size of 6.05 nm. The porous structure of
nano-zeolite was effectively utilized to incor- porate essential macro
and micronutrients that are released slowly to the plant depending
upon their affinity to the zeolite. The syn- thesized materials were
characterized using physical parameters, powder XRD, FT-IR, AFM,
SEM/EDX, TGA and DSC to get insight into the properties,
morphology and structure. Water absorbance, swelling ratio,
equilibrium water content, salt index and water retention studies
showed good water holding capacity that can enhance soil condition
without imparting negative impacts. Further the slow release
studies confirm the gradual supply of nutrients to the plants over a
large period of time that helps in reducing leaching impacts of the
traditional fertilizers.
Acknowledgment
The financial support of PCSIR Labs Complex, Lahore, Pakistan
and Higher Education Commission (HEC), Pakistan under Indige-
nous PhD Fellowship for 5000 Scholars, Phase - ll is greatly
acknowledged for this study.
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