Journal of Solid State Chemistry 302 (2021) 122446

Contents lists available at ScienceDirect

Journal of Solid State Chemistry

journal homepage: www.elsevier.com/locate/jssc

Fabrication of lanthanum linked trimesic acid as porous metal organic

frameworks for effective nitrate and phosphate adsorption
Ilango Aswin Kumar a, Antonysamy Jeyaseelan a, Natrayasamy Viswanathan a, *, Mu. Naushad b,
Artur J.M. Valente c
a
Department of Chemistry, Anna University, University College of Engineering - Dindigul, Reddiyarchatram, Dindigul, 624 622, Tamilnadu, India
b
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia
c
CQC, Department of Chemistry, University of Coimbra, 3004 - 535, Coimbra, Portugal

A R T I C L E I N F O A B S T R A C T

Keywords: The potable water crisis worldwide may lead to the detoxification of aquatic pollutants which becomes the
Lanthanum research hotspot. The construction of metal-organic frameworks (MOFs) serves as the promising adsorbent ma-
Trimesic acid terial for the efficient removal of toxic ions from aqueous solution. Hence, the present research article covers the
NO
3

3 and PO4 adsorption
development of lanthanum linked trimesic acid (LTA) based MOFs for soluble nitrate (NO
3 ) and phosphate
LTA MOFs reuse
(PO3

4 ) adsorption from water. The developed LTA MOFs were characterized by numerous instrumentation
techniques like FTIR, SEM, EDAX, XRD, TGA, DTA and BET studies. The function of LTA MOFs declares the
enhanced removal properties on NO
3

3 /PO4 adsorption at batch condition. The adsorption mechanism of LTA
MOFs was explored along with kinetics, isotherms and thermodynamic studies. The emerging trends of LTA MOFs
for controlling the water quality parameters were also discussed at field level. The synthesized LTA MOFs could be
reused many cycles for adsorption technique.

1. Introduction utilizations which results for recovering specific and complex ions during
adsorption studies [11]. The significant factor for constructing MOFs on
The manufacturing and farming industries has largely produced the water treatment has increased owed to its controlled pore size, hydro-
nitrogen (N) and phosphorous (P) as their primary effluents [1]. Often, philicity (affinity to water) and distinctive structural assortment [12].
the severe health disease namely methemoglobinemia (blue baby syn- The active metal sites of MOFs act as the Lewis acid/redox part and hence
drome) is occurred when the human intakes the drinking water with it is used as the solid phase adsorbents for the detoxification of ion-
presence of soluble NO
3 species [2]. Conversely, the unconditional s/pollutants in aqueous system. Nowadays, MOFs and the modified MOFs
release of fertilizers (NO
3

3 and PO4 ) from agricultural and industrial such as NiO/Ni@C400 (Ni-MOF) [13], ZnO/ZnFe2O4/C (MOF-5) [14],
fields ends with the aquatic nutrients pollution which is a global envi- NPC@CNT (MOF-199) [15], CuZn@C-0.05 (ZIF-8) [16], isostructural
ronmental problem. Moreover, the ejection of nutrients results in the MOFs (MOF-Ni, MOF-Co, and MOF-Cu) [17], ZnO@C–600 N (MOF-5)
eutrophication of the drinking water which closes to the greenhouses [3]. [18], Ag2(H3ddcba)(4,40 -bipy)2 [19], etc., have been widely utilized for
The removal techniques such as electro-coagulation [4], membrane the numerous toxic contaminants removal.
process [5], ion-exchange [6], adsorption [7], bio-treatment [8], etc., Saleh et al., have studied 2D Co(II) based MOFs namely [(1,2-DPE)
have investigated to reduce the NO
3

3 and PO4 concentration in water Co2Cl2]n (HT-1) for methyl orange (MO) and methylene blue (MB)
below the tolerance limits as 45 and 0.5 mg/L respectively [9]. By adsorption from water [20]. The 1,2-di(4-pyridyl)ethylene (1,2-DPE)
considering the eco-friendly and cost-effective with rapid removal pro- was utilized as the organic polymer and the solvothermal method was
cess, the current research was optimized with the adsorption technique encouraged for the synthesis process which gives the maximum adsorp-
[10]. tion efficiency. It was interesting to note that the aromatic electrons of
The structural connection of the metal organic frameworks (MOFs) HT-1 were coordinated with Nþ of MB via strong cation-Π-interaction
make use of the chemistry such they can be refrained for desired along with SO
3 of MO via weak anion-Π-interaction which almost gives

* Corresponding author.
E-mail addresses: aswinmariya@gmail.com (I. Aswin Kumar), drnviswanathan@gmail.com (N. Viswanathan).

https://doi.org/10.1016/j.jssc.2021.122446
Received 3 June 2021; Received in revised form 12 July 2021; Accepted 19 July 2021
Available online 20 July 2021
0022-4596/© 2021 Elsevier Inc. All rights reserved.
I. Aswin Kumar et al. Journal of Solid State Chemistry 302 (2021) 122446

97 % of dyes recovery. 2.2. Preparation of LTA MOFs

Likewise, Yang et al., have investigated Zn based MOFs using ZIF-8
precursor with uniform hierarchical pores for formaldehyde adsorption The preparation of LTA MOFs is shown in Fig. 1.
which possess the removal capacity of 17.57 mg/g at 12.84 % of Zn
atomic mass [21]. The oxygen containing functional groups and Zn 2.3. Adsorption experiments
reactive sites on the MOFs had the potential affinity for the formaldehyde
capture towards it. Moreover, the hierarchical porous nature may pro- The synthesized LTA MOFs was immersed in NO
3

3 and PO4 solution
duce the necessary space to move through which also enhances the respectively which contains the primary concentration upto 100 mg/L at
formaldehyde adsorption by the way of strong hydrogen bonding. 10–60 min. For an experimental set up, the above mixture was shaken,
Similarly, He et al., have investigated Ce based MOFs derived from Ce(1, filtered through centrifugation at the respective time interval and their
3,5-BTC)(H2O)6 for the effective adsorption (189.4 mg/g) of PO3
4 in concentration was measured on UV–vis spectrophotometer. On the other
wide ranges of pH [22]. The BET surface area of the synthesized MOFs side, the optimization of adsorption operating features like effect of nu-
was found to be 101.0 m2/g and hence it provides the large space for trients pH, MOFs dosage, contact period of time, contending anionic
PO3
3

4 in order to engage its more active sites. The PO4 removal was species, temperature and selectivity towards removal performances was
majorly occurred by way of electrostatic attraction, surface precipitation executed. To fix the wide range of pH, about 0.1 M HCl/NaOH was uti-
and ligand exchange based on the pH of PO3
4 solution. lized. To check the change of initial ions concentration from 80 to 120
Trimesic acid (TA) is commonly known to be benzene-1,3,5- mg/L at an assorted temperature scale of 303–323 K by the means of
tricarboxylic acid, having the structural (linear) formula of isotherms, kinetic and thermodynamic parameters works were carried
C6H3(CO2H)3. TA is a crystalline organic material which is linked with 4- out. The water uptake performance of LTA MOFs was determined using
pyridone [23]. It has a network gathered by hydrogen bonds of –COOH in swelling study (Eqn. (1)). The SC and removal efficiency of MOFs was
bulk. It is highly stable at aqueous medium (H2O), methanol (CH3OH) given by Eqns. (2) and (3) respectively.
and ethanol (CH3CH2OH). It was mainly utilized as the water based
gel/coating material, plastic, cross-linker, membrane for desalination, Ws
W d
Swelling ratio ð%Þ ¼ 100 (1)
poxy curing agent, etc. To spotlight on adsorption, the reactive functional Wd
groups of –COOH of TA has an ability to interact with the Lewis metals
where Ws and Wd are weight of the swollen and dry LTA MOFs (g)
(Zr4þ, La3þ, Ce3þ, Fe2þ, etc.) which results in 2D type of MOFs for con-
respectively.
taminants recovery. Moreover, from the review of literature La3þ assisted
TA based MOFs were not yet applied for NO
3

3 and PO4 adsorption which
has become the current research hotspot.
Herein the present investigation is aimed to develop LTA MOFs for
NO
3

3 and PO4 adsorption from water. The retention time was fixed to
find the total reaction period taken for the successful adsorption by MOF.
The batch wise applied LTA MOFs underwent the reusable studies. The
numerous chemical instrumentations were also scrutinized in order to
ensure the variable stability of the synthesized LTA MOFs towards the
adsorption performance. In addition to batch studies, the kinetic and
isotherms along with thermodynamic parameters of LTA MOFs was
investigated as primary focus. The effect of LTA MOFs on nutrients
retention at field contaminated water sample was also investigated.

2. Experimental section

2.1. Materials

The details of chemicals by way of IUPAC name, molecular formula,

CAS registry, purity and procured detail of the materials are demon-
strated in Table 1. The typical NO
3

3 /PO4 solution was prepared by the
respective dissolution of anhydrous KNO3 (1.6305 g) and anhydrous
KH2PO4 (1.4329 g) in 1000 mL of double distilled water. Fig. 1. Preparation of LTA MOFs.

Table 1
IUPAC, CAS registry, molecular weight, purity and procured details of the materials.
S.No. IUPAC systematic name CAS registry number Molecular weight (g mol
1) Sample purity (%) Procured detail

1 Benzene-1,3,5-tricarboxylic acid (Trimesic acid) 554-95-0 210.14 99.99 Merck, India

2 N,N-dimethylformamide 68-12-2 73.09 98.00 Merck, India
3 Ammonium metavanadate 7803-55-6 116.98 98.00 Merck, India
4 Ammonium heptamolybdate tetrahydrate 12054-85-2 1235.9 99.00 Merck, India
5 Sodium fluoride 7681-49-4 41.99 99.99 Merck, India
6 Sodium sulphate 7757-82-6 142.04 99.00 Merck, India
7 Potassium nitrate 7757-79-1 101.10 99.00 Merck, India
8 Potassium dichromate 7778-50-9 294.18 67.40 Merck, India
9 Sodium chloride 7647-14-5 58.44 99.00 Merck, India
10 Sodium bicarbonate 144-55-8 84.01 99.70 Merck, India
11 Potassium dihydrogen phosphate 7778-77-0 136.08 98.00 Merck, India

2
I. Aswin Kumar et al. Journal of Solid State Chemistry 302 (2021) 122446

Ci
Ce Table 2
Sorption capacity ðSCÞ ¼ V (2)
m Instrumentation details for LTA MOFs.
Details of Name of the instrument Model
Ci
Ce characterization
Removal efficiency ð%Þ ¼ 100 (3)
Ci Crystallinity of LTA- XRD (X-ray diffraction) X'pert 173 PRO
MOFs PAN-alytical
where Ci and Ce are the initial and equilibrium concentration of NO

and 3 BET textures of LTA- BET (Brunauer-Emmett-Teller) NOVA 1000
PO3
4 (mg/L) respectively at time (min), m is LTA MOFs dosage (g) and V MOFs
is volume (L) of the nutrients solution. Elementals of LTA-MOFs EDAX (Energy dispersive X-ray Bruker Nano
analysis) GMBH
Thermal stability of LTA- TGA (Thermogravimetric Universal V4.5A
2.4. Analysis and instrumentation MOFs analysis) TA
Chemical composition of DTA (Differential thermal Universal V4.5A
To analyze NO
3

3 and PO4 concentration by UV–Vis spectrophotom-
LTA-MOFs analysis) TA
Surface morphology of SEM (Scanning electron Vega3 Tescan
eter (Spectroquant Pharo 300, Merck) was utilized and fixed at 202 and
LTA-MOFs microscope)
400 nm respectively. The molybdate-vanadate reagent was utilized for Functional groups of LTA- FTIR (Fourier transform infrared) JASCO-460 plus
PO3

4 concentration. The pH drift method was used to determine pH at MOFs spectrometer
zero point charge (pHzpc) of LTA MOFs [24]. To measuring the pH of NO
3
and PO3
4 solution by Thermo Orion Benchtop multiparameter kit
(VERSA STAR92) with pH electrode. To improving the quality of LTA MOFs, NO
3

3 and PO4 adsorbed LTA MOFs having numerous sig-

drinking water such as Cl
, hardness and total dissolved solids (TDS) was nificant FTIR bands. Referring to that, the –OH groups (H2O) of LTA
analyzed using standard methods [25]. The characterization details of MOFs were detected at 3413 cm
1. Mainly the presence of –COOH
LTA MOFs are shown in Table 2 as follows. (-COO-) in LTA MOFs give the strong stretching vibrations at 1615 cm
1
[28]. The sharp characteristic FTIR band of La–OH was appeared at 1118
cm
1 which clearly shows the interaction of COO
…. .La3þ to produce
2.5. Statistical tools
the effective LTA MOFs. In addition, the aromatic ring (benzene) closure
of TA linker was occurred at 716, 766, 877 and 1074 cm
1 [29]. At the
The experimental data was computed using Microcal Origin (version
same time, after the adsorption process, the FTIR bands of this aromatic
15) software. Moreover, regression correlation coefficient (r), standard
ring system were slightly reduced which shows they somewhat involved
deviation (sd) and chi-square analysis (χ2) was fitted with the appro-
in adsorption whereas the FTIR bands of La3þ (1118 cm
1) was deeply
priate model towards nutrients adsorption.
reduced (almost diminished) as clearly marked in FTIR spectra of the
respective NO
3

3 and PO4 adsorbed LTA MOFs may confirms the feasible
3. Results and discussion
NO
3 and PO 3

4 adsorption process. The reason for this reduced intensity
may govern from the electrostatic attraction mechanism occurred be-
3.1. Instrumentation studies
tween the La3þ and NO
3

3 /PO4 [30]. Moreover, the strong FTIR band of
NO
3 and PO 3

4 loaded LTA MOFs at 1636 and 1629 cm
1 was noticed
3.1.1. TGA and DTA analysis – O and O– – P–OH respectively.
due to the deformation (vibration) of N–
TGA and DTA curve of the developed LTA MOFs was investigated in
Moreover, the fresh FTIR bands at 1380 and 598 cm
1 in FTIR spectra of
the temperature ranges of 0–800  C with the rate of 10  C/min. The first
PO3
3

4 adsorbed LTA MOFs which further confirm PO4 adsorption onto
weight loss was occurred due to H2O molecules of LTA MOFs in the
the synthesized LTA MOFs.
ranges of 90–150  C. Further, the cleavage of N,N-dimethylformamide
solvent was noticed at 280  C [26]. However, almost the thermal stability
3.1.4. SEM and BET studies
was maintained over the temperature ranges of 0–800  C which may
The surface topography of the developed LTA MOFs was investigated
confirms the synthesized LTA MOFs can be used in the wide range of
using SEM analysis which is demonstrated in Fig. 3a–d. SEM picture of
temperature condition. Moreover, the quantitative analysis of the
LTA MOFs was taken at 50 μm which has a crystalline and flower-like
chemical composition of LTA MOFs during heat change measurement
surface (Fig. 3a). The close vision of the same was taken at 10 μm
was imprinted using DTA. It was found that the heat flow of
25 to
13
which has the needle like surface along with active pores (Fig. 3b). Later,
mW/mg the weight losses with purpose were observed (Fig. 2a).
the crystalline nature of LTA MOFs was almost reduced after NO
3 and


PO3
3

4 adsorption as shown in SEM pictures of NO3 and PO4 adsorbed
3.1.2. XRD studies
LTA MOFs (Fig. 3c and d) respectively.
The crystalline composition of LTA MOFs was determined using XRD
BET structural properties such as specific surface area, total pore
studies. The synthesized LTA MOFs is a monoclinic crystal system which
volume and average pore width of the synthesized LTA MOFs was
possess the numerous enhanced crystalline peaks at 2Ɵ such as 22.72 ,
investigated using N2 adsorption isotherms at atmospheric condition
29.38 , 31.39 , 35.36 , 38.90 , 42.46 , 46.58 , 47.80 , 55.37 , 56.52 ,
which are shown in Fig. 4. It was found that the synthesized LTA MOFs
59.91 , 61.48 , 62.33 , 63.49 and 66.45 respectively (Fig. 2b). The
possesses the good numbers of specific surface area of 129.03  0.01 m2/
interaction of organic linker and metal cluster prefers to produce the
g. However, it was found that the total pore volume of LTA MOFs was
crystalline peaks under X-rays. Due to the higher crystalline behaviour,
found to be lower as of 1.24  0.03 cm3/g. The BET specific surface area
the active sites of LTA MOFs can be easily attracted by higher initial
would be increased at the same time total pore volume must be
concentration of NO
3

3 and PO4 species [27]. Moreover, in PXRD pattern
decreased. Moreover, the average pore width of LTA MOFs was observed
of LTA MOFs, most of the peaks were observed as highly intensive and
as 4.063  0.02 nm which may be easily attracted by NO
3 and PO4
3

sharp which shows the synthesized LTA MOFs is highly crystalline and
species.
porous in nature which ensures the enhanced stability of the synthesized
LTA MOFs for the adsorption studies.
3.1.5. EDAX and swelling studies
The element distribution of synthesized LTA MOFs was detected
3.1.3. FTIR investigation
using EDAX analysis which contains the significant elements such as O, C
The background material namely potassium bromide (KBr) was
and La with the atomic % of 41.20  0.15, 30.04  0.01 and 27.09 
applied for the functional group investigations of LTA MOFs at the
0.03% respectively (Fig. 5a). In EDAX of NO
3 adsorbed LTA MOFs, the
wavenumber ranges of 4000–400 cm
1. Fig. 2c exhibits FTIR spectra of

3
I. Aswin Kumar et al. Journal of Solid State Chemistry 302 (2021) 122446

Fig. 2. (a) TGA and DTA curves of LTA MOFs at 0–800  C, (b) XRD spectra of LTA MOFs at 10–80 2Ɵ (degree) ranges and (c) FTIR spectra of (a) LTA MOFs, (b) NO

3
adsorbed LTA MOFs and (c) PO3
4 adsorbed LTA MOFs.

fresh N peak was observed with the atomic % of 7.13  0.05% whereas lead to attain the maximum removal capacity. In addition, PO3
4 SC was
the O, C and La % was found to be decreased as of 36.08  0.10, 28.76  found higher than NO
3

3 SC. It may be attributed that the aquatic PO4 has
0.01 and 25.07  0.16% may confirms its adsorption. In EDAX of PO
4 many structural forms at widest pH ranges than univalent NO
3 . Hence,
adsorbed LTA MOFs, the new P peak was observed as 13.70  0.01%. It lots of chances for PO3

4 to stick onto the MOFs surface. Finally, the po-
was also cleared that the atomic % of P was higher than N (Fig. 5b and c). tential LTA MOFs were exploited for further retention studies at the fitted
As evident from the result that PO

4 was mostly occupied by MOFs surface contact time of 30 min.
than NO
3 species. The water absorption character of the synthesized LTA
MOFs was performed using swelling studies and it was noted as 6.83  3.3. Influence of dosage
0.03%. From this, only the mentioned % of active sites of MOFs was
occupied by H2O molecules which further confirm that the remaining The varied dosage ranges (0.025–0.15 g) of LTA MOFs were chosen.
active sites are meant for the adsorption of NO
3

3 and PO4 species in The main factor of dosage study is that as the number of the vacant sites
water. of MOFs increases, the adsorption capability also increases until filled.
Hence, the NO
3 SCs of LTA MOFs was increased from 19.72  0.03 to
3.2. Influence of shaking period 50.09  0.01 mg/g with respect of 0.025–0.15 g whereas PO3
4 SCs was
much increased from 23.87  0.02 to 63.01  0.05 mg/g on the same
Most of the developed materials in adsorption may have the good dosage condition (Fig. 6b). Afterward, SC reached the equilibrium stage
removal capacity but they often fall with the longer reaction time. If the because of no free active space of MOFs for the interaction of NO
3 and
desired time of adsorption was identified, it would be easy to fix the PO3

4 . It is also clear that within 0.1 g of LTA dose, the most occupation of
system for the successful removal. About 0.1 g of LTA MOFs was poured NO
3

3 and PO4 was occurred [31]. At last, 0.1 g of LTA MOFs was
into respective NO
3

3 and PO4 (100 mg/L) solutions, shaken at 10–60 approached for NO
3

3 /PO4 adsorption studies.
min and then Ce was calculated. It was accomplished that the SCs of LTA
MOFs were observed as 49.731  0.05 and 62.806  0.02 mg/g 3.4. Influence of pH medium
respectively within a quick equilibrium time period of 30 min (Fig. 6a).
The La3þ was formed as a surface complex with –COOH groups of TA and The pH is a critical factor in adsorption studies, because it often in-
shaped as La(NO3)3 and La(PO3
4 ) in the aqueous solution which may fluences the ionization of NO
3

3 and PO4 in aqueous solution and also

4
I. Aswin Kumar et al. Journal of Solid State Chemistry 302 (2021) 122446

Fig. 3. (a & b) SEM images of LTA MOFs at 50 and 10 μm respectively, (c) NO

3 adsorbed LTA MOFs at 10 μm and (d) PO4 adsorbed LTA MOFs at 10 μm.
3

Fig. 4. (a) N2 adsorption/desorption isotherm of LTA MOFs at 77 K and (b) pore size distribution of LTA MOFs.

modifies the surface property of the synthesized LTA MOFs. With the 3.5. Influence of contending anions
raise of pH 3–11 using 0.1 M HCl/NaOH, the diverse pH effect was noted
as accounted in Fig. 6c. The enhanced NO
3 removal was occurring on pH The competing anions such as sulphate (SO2


4 ), chromate (HCrO4 ),
5 whereas the maximum PO3
4 was adsorbed at pH 7. This was recon- bicarbonate (HCO



3 ), chloride (Cl ) and fluoride (F ) which having the
firmed by pHzpc value (6.20) of LTA MOFs (Fig. 6d). The suspended LTA good bonding affinity on MOFs surface were taken in this study (Fig. 6e).
MOFs possess the positive surface charge below pHzpc, therefore the Additionally, the increasing the concentration of these competitors may
protonated LTA MOFs remove both NO
3

3 /PO4 by way of electrostatic decrease the NO
3

3 /PO4 SC. Hence, co-anions concentration was taken as


attraction. On the other side, it was inferred that as pH < pHzpc, the net 200 mg/L while NO3 /PO3
4 was in use as 100 mg/L. The affinity of an-
surface charge of LTA MOFs becomes negative (OH
ions) means that the ions on MOFs getting increased as the surface charge (positive) of MOFs
competition occurred between OH
and respective NO
3

3 /PO4 in solu- is higher indicating the formation of electrostatic attraction on MOFs
tion to form adsorptive interaction with LTA MOFs [32]. Moreover, the with that of the respective co-anions. The result demonstrates that even
synthesized MOFs were stable at widest pH ranges which ensures the double the concentration of HCO
3 the competition was not achieved for
MOFs can be easily adopted for industrial effluent treatments. NO
3


3 /PO4 . The presence of HCrO4 in aqueous solution was almost the

5
I. Aswin Kumar et al. Journal of Solid State Chemistry 302 (2021) 122446

Fig. 5. EDAX spectra of (a) LTA MOFs, (b) NO
3

3 adsorbed LTA MOFs and (c) PO4 adsorbed LTA MOFs.

same as the pH of the nutrients solution but its contending ability was not mechanism approach should be clarified on different ions such as HCrO
4,
effective. In addition, the F
and Cl
possess extended contending ability. F
, SO2


3


4 , Cl , HCO3 in addition to PO4 and NO3 . From Fig. 6f, it was
Typically, the divalent anions are good competitor than monovalent clear that the synthesized LTA MOFs has an enhanced SC of 49.73 and
since they have greater charge density in order to adsorb the MOFs 62.80 mg/g on NO
3


3 and PO4 respectively. In the case of Cl , the sta-
surface sites [33]. Taking this, among the co-anions SO2
4 possess the bility was maintained at acidic pH i.e. pH~3. In this situation, the metal
enriched contending nature during NO
3

3 and PO4 adsorption since SO4
2

loaded adsorbents would not be an effective and hence the Cl
was not
3

has more or less ionic radii with that of PO4 . At the same time, the efficiently surrounded onto the MOFs surface at higher acidic pH con-
synthesized LTA MOFs possess the potential towards nutrients adsorption dition whereas the HCO
3 was stabled at basic pH of 9 but its adsorption
studies. was struggled by basic OH
ions at this condition [34]. The pHzpc of LTA


MOFs and the PO3
4 and NO3 solution pH was almost same hence the


3.6. Influence of selectivity studies protonated LTA MOFs surface was easily attracts the both PO3
4 and NO3
by the way of electrostatic attraction. In addition, the SCs of LTA MOFs
It is essential for the synthesized LTA MOFs how it is particularly towards HCrO


4 and F were somewhat extended. At the same time the


removes the NO
3

3 and PO4 or if it has selectivity means then the
divalent SO2

4 possesses the considerable SC next to PO3
4 and NO3 . Most

6
I. Aswin Kumar et al. Journal of Solid State Chemistry 302 (2021) 122446

Fig. 6. Effect of (a) contact time, (b) dosage, (c) pH, (d) pHzpc, (e) co-ions and (f) selectivity studies of LTA MOFs on NO
3

3 and PO4 SC.

Table 3
Isotherms of LTA MOFs for NO
3

3 and PO4 adsorption.

Isotherms Parameters NO

3 PO3-
4

303 K 313 K 323 K 303 K 313 K 323 K

Freundlich 1/n 0.268  0.01 0.269  0.05 0.273  0.04 0.506  0.03 0.508  0.10 0.510  0.01
n 3.037  0.03 3.039  0.11 3.041  0.02 4.975  0.03 4.978  0.09 4.979  0.01
k1/n
F (mg/g) (L/mg) 29.401  0.01 29.406  0.09 29.409  0.05 37.517  0.03 37.519  0.01 37.520  0.09
r 0.942  0.05 0.943  0.07 0.949  0.01 0.995  0.01 0.997  0.11 0.998  0.05
sd 2.073  0.07 2.075  0.03 2.079  0.02 4.076  0.01 4.078  0.03 4.080  0.05
χ2 0.734  0.02 0.736  0.05 0.738  0.01 0.304  0.09 0.306  0.01 0.308  0.07
Langmuir Qo(mg/g) 49.721  0.03 49.990  0.01 50.014  0.02 61.090  0.07 62.731  0.01 62.812  0.03
b (L/g) 0.035  0.09 0.037  0.10 0.039  0.11 0.083  0.05 0.086  0.01 0.087  0.10
RL 0.892  0.02 0.893  0.01 0.896 0.04 0.971  0.01 0.973  0.13 0.975  0.02
r 0.991  0.01 0.993  0.05 0.997  0.03 0.945  0.08 0.947  0.03 0.948  0.06
sd 1.682  0.09 1.685  0.13 1.689  0.01 7.003  0.11 7.006  0.01 7.007  0.03
χ2 0.127  0.01 0.129  0.03 0.130  0.02 0.782  0.03 0.783  0.02 0.789  0.06
Dubinin - Radushkevich kDR (mol2/J2) 5.09E-02 5.10E-02 5.13E-02 7.92E-02 7.93E-02 7.95E-02
Xm (mg/g) 19.521  0.02 19.525  0.01 19.527  0.15 26.069  0.07 26.070  0.05 26.073  0.01
E (kJ/mol) 8.045  0.01 8.091  0.01 8.150  0.02 8.726  0.01 8.731  0.06 8.820  0.01
r 0.903  0.06 0.904  0.02 0.905  0.01 0.829  0.03 0.830  0.01 0.831  0.08
sd 3.024  0.07 3.026  0.05 3.028  0.01 6.120  0.09 6.121  0.03 6.125  0.01
χ2 0.538  0.13 0.539  0.07 0.541  0.06 0.509  0.03 0.510  0.01 0.512  0.19

cases, the selectivity of LTA MOFs mainly towards NO
3

3 and PO4 than physisorption mechanism. From, D-R the E value was nearer to 8–9
other anions/oxyanions. kJ/mol which is said to be physisorption of LTA MOFs with that of
NO
3


3 /PO4 . Moreover, the Langmuir isotherm support the NO3 retention
via monolayer coverage on homogenous surface while Freundlich
3.7. Isotherms of LTA MOFs
isotherm supports the PO3
4 retention via multilayer coverage on het-
erogeneous surface coverage which supports from the higher r and lower
The synthesized LTA MOFs was established to evaluate the maximum
χ2 and sd values as presented in Table 3.
NO
3 and PO4
3

SC through Langmuir [35], Freundlich [36] and
Dubinin-Radushkevich (D-R) [37] isotherms at 303, 313 and 323 K. From
Table 3, Freundlich adsorption intensity (n) i.e. n > 1 and 1/n i.e. 0 > 3.8. Thermodynamic parameters of LTA MOFs
1/n > 1 proclaim the favorable adsorption condition which confirms the
good interaction of LTA MOFs onto the both NO
3

3 and PO4 . The sepa- The characteristic features of adsorption system at the assorted re-
ration factor (RL) from Langmuir between 0 < RL < 0 explores the action temperature (303, 313 and 323 K) was investigated using ther-
feasibility of the adsorption system. Additionally, the measured Qo value modynamic parameters such as standard entropy change (ΔS ), Gibbs
was getting increased as of raising the temperature of the system. The free energy change (ΔG ) and standard enthalpy change (ΔH ) [38]. The
flow of adsorption mechanism was governed using the D-R isotherm in absorption of enthalpy (heat energy) from closest surrounding during
which the calculated mean adsorption energy (E) value i.e. if its >10 adsorption process is known to be endothermic in which ΔH is positive
kJ/mol means that chemisorption and <10 kJ/mol ensures the for this case. Likewise, the ΔH is positive for LTA MOFs and hence the

7
I. Aswin Kumar et al. Journal of Solid State Chemistry 302 (2021) 122446

Table 4 Tables 5 and 6 respectively. The concentration was taken as 80–140 mg/
Thermodynamic parameters of LTA MOFs. L at 303, 313 and 323 K. By considering the higher r value and lower sd
Thermodynamic parameters NO

3 PO3-
4
value on the both models, it was concluding that the pseudo-second-
o order and intraparticle diffusion models were suitable kinetics for NO
3
ΔG (kJ/mol) 303 K
1.862  0.04
2.098  0.01
313 K
1.865  0.01
2.101  0.03 and PO3
4 adsorption process [41,42]. From this, it was driven that the
323 K
1.869  0.07
2.136  0.01 physical electrostatic attraction was majorly involved in the adsorption
ΔHo (kJ/mol) 18.024  0.03 23.618  0.05 system.
ΔSo (J/mol K) 0.421  0.01 0.304  0.01

3.10. Removal mechanism of LTA MOFs and comparision studies

energy is absorbed during interaction with NO
3

3 /PO4 ions. This was also

confirmed from the increase in Q value with respect of increasing re- The removal mechanism of LTA MOFs on NO
3

3 and PO4 was found to

action temperature which declares the endothermic adsorption system be electrostatic attraction as presented in Fig. 7. The –COOH groups of
[39]. In addition, the ΔH value (18.024  0.03 and 23.618  0.05 benzene-1,3,5-tricarboxylic acid (Trimesic acid) can be formed as
kJ/mol) for NO
3
-COO-Hþ which may easily interact with La3þ and formed as -COO-
3 and PO4 respectively ensures the physical adsorption
nature of nutrients onto LTA MOFs. As clearly presented in Table 4, the …...La3þ. The presence of La3þ in LTA MOFs make the higher stability for
consistent decrease in ΔG at varied temperature explores the irrevers- the synthesized MOFs in which La3þ plays the strong acidic character
ible, spontaneous and feasible adsorption process. It was interested that which often interacts with NO
3

3 and PO4 respectively by the way of

the ΔS value is close to zero (0.421  0.01 and 0.304  0.01 J/mol K) electrostatic attraction [43]. The removal mechanism was further
for NO
3
confirmed by FTIR and EDAX studies. Mainly, FTIR bands of La3þ were
3 and PO4 respectively may due to the no movement of the
particles onto the MOFs surface after the completion of adsorption pro- found to be diminished in FTIR spectra of NO
3

3 and PO4 adsorbed LTA

cess [40]. MOFs may confirm the interaction of La3þ with that of NO
3 and PO4
3

respectively. Moreover, in EDAX the freshly appeared N and P peak in

EDAX images of NO
3

3 and PO4 adsorbed LTA MOFs may also confirm the

3

3.9. Kinetics of LTA MOFs NO3 and PO4 adsorption.
Comparing the adsorption capacity of the synthesized MOFs with
The rapid adsorption process may directly affect the adsorption effi- other commercial materials may often be considered as necessary in the
ciency of the MOFs. In this present investigation, the maximum SC was adsorption process. The assessment gives the ability to make use of
reached at 30 min and after increasing the reaction time does not influ- synthesized MOFs at industrial scale. As evident from Table 7 that the
ence the SC. This may be due to the less available sites of the MOFs. The synthesized MOFs possesses an enhanced removal capacity as compared
improved kinetic performances indicate the superior electrostatic inter- with other materials. The reason for high removal capacity may be due to
action on the MOFs surface. The NO
3

3 and PO4 SC were increased with
the presence of La3þ in MOFs which makes it perform as Lewis acid for
respect to its salts concentration which leads to the increase in sticking of attracting the Lewis bases such as NO
3

3 and PO4 . At last, it was decided
ions onto the surface sites along with decreasing the water content on the that the synthesized LTA MOFs was a prominent material for the
sites. To study the adsorption force, the reaction and diffusion based detoxification of aquatic contaminants.
kinetic models were executed and their parameters were presented in

Table 5
Kinetics of LTA MOFs for NO

3 adsorption at 303, 313 and 323 K.

Kinetic Parameters 303 K 313 K 323 K

models
80 mg/L 100 mg/ 120 mg/ 140 mg/ 80 mg/L 100 mg/ 120 mg/ 140 mg/ 80 mg/L 100 mg/ 120 mg/ 140 mg/
L L L L L L L L L

Pseudo-first- kad (min
1) 0.006  0.009  0.013  0.015  0.019  0.021  0.023  0.025  0.019  0.029  0.031  0.034 
order 0.03 0.07 0.05 0.07 0.05 0.09 0.04 0.03 0.02 0.05 0.02 0.01
r 0.913  0.914  0.913  0.915  0.929  0.931  0.932  0.933  0.938  0.940  0.943  0944 
0.01 0.06 0.02 0.09 0.004 0.03 0.01 0.08 0.14 0.06 0.02 0.08
sd 0.562  0.563  0.567  0.569  0.624  0.626  0.629  0.630  0.673  0.675  0.679  0.680 
0.03 0.01 0.04 0.03 0.05 0.02 0.06 0.07 0.03 0.01 0.02 0.14
Pseudo- qe (mg/g) 37.125 39.127 39.129 39.130 41.024 43.026 43.028 43.031 45.027 47.721 47.723 47.725
second-  0.01  0.06  0.04  0.07  0.08  0.09  0.05  0.01  0.01  0.03  0.02  0.05
order k (g/mg 0.076  0.082  0.083  0.084  0.081  0.091  0.092  0.094  0.083  0.098  0.097  0.099 
min) 0.09 0.04 0.05 0.09 0.11 0.03 0.09 0.17 0.01 0.06 0.08 0.10
h (mg/g 7.216  10.246 10.248 10.249 7.918  11.672 11.679 11.682 8.264  13.643 13.646 13.649
min) 0.05  0.02  0.01  0.03 0.11  0.09  0.19  0.01 0.08  0.02  0.01  0.06
r 0.991  0.992  0.995  0.996  0.997  0.998  0.998  0.997  0.998  0.999  0.999  0.999 
0.02 0.08 0.01 0.02 0.03 0.04 0.01 0.06 0.02 0.02 0.04 0.11
sd 0.065  0.066  0.069  0.070  0.098  0.102  0.106  0.105  0.308  0.309  0.312  0.315 
0.06 0.05 0.03 0.01 0.10 0.13 0.16 0.01 0.04 0.03 0.07 0.01
Particle kp (min
1) 0.020  0.059  0.061  0.060  0.023  0.069  0.071  0.070  0.029  0.085  0.086  0.089 
diffusion 0.05 0.03 0.01 0.04 0.02 0.01 0.07 0.09 0.11 0.08 0.01 0.05
r 0.861  0.862  0.865  0.866  0.889  0.890  0.892  0.895  0.897  0.899  0.898  0.901 
0.03 0.01 0.05 0.03 0.05 0.02 0.06 0.02 0.07 0.02 0.01 0.09
sd 0.862  0.866  0.868  0.869  0.997  0.999  1.024  1.026  1.895  1.897  1.898  1.899 
0.09 0.02 0.01 0.09 0.15 0.13 0.03 0.08 0.02 0.08 0.07 0.01
Intraparticle ki (m/g 0.106  1.862  1.865  1.869  0.109  1.875  1.878  1.881  0.129  1.906  1.908  1.912 
diffusion min0.5) 0.01 0.09 0.01 0.11 0.12 0.03 0.09 0.05 0.03 0.01 0.09 0.02
r 0.989  0.988  0.990  0.991  0.993  0.995  0.993  0.996  0.997  0.995  0.998  0.999 
0.03 0.12 0.06 0.01 0.02 0.03 0.18 0.16 0.01 0.08 0.04 0.01
sd 0.385  0.387  0.389  0.390  0.456  0.457  0.459  0.460  0.493  0.497  0.498  0.499 
0.03 0.01 0.07 0.01 0.08 0.03 0.04 0.01 0.05 0.03 0.05 0.06

8
I. Aswin Kumar et al. Journal of Solid State Chemistry 302 (2021) 122446

Table 6
Kinetics of LTA MOFs for PO3

4 adsorption at 303, 313 and 323 K.

Kinetic Parameters 303 K 313 K 323 K

models
80 mg/L 100 mg/ 120 mg/ 140 mg/ 80 mg/L 100 mg/ 120 mg/ 140 mg/ 80 mg/L 100 mg/ 120 mg/ 140 mg/
L L L L L L L L L

Pseudo-first- kad (min
1) 0.004  0.019  0.021  0.023  0.006  0.026  0.029  0.031  0.009  0.034  0.035  0.037 
order 0.13 0.08 0.13 0.01 0.60 0.12 0.01 0.09 0.01 0.06 0.09 0.03
r 0.905  0.913  0.916  0.917  0.909  0.942  0.945  0.946  0.911  0.946  0.947  0948 
0.09 0.11 0.07 0.15 0.02 0.16 0.09 0.10 0.16 0.07 0.01 0.10
sd 0.216  0.260  0.263  0.265  0.219  0.268  0.269  0.276  0.221  0.279  0.280  0.281 
0.03 0.07 0.09 0.06 0.11 0.04 0.13 0.03 0.08 0.10 0.02 0.04
Pseudo- qe (mg/g) 60.257 61.083 61.089 61.092 60.976 63.093 63.102 63.109 61.082 65.069 65.073 65.096
second-  0.03  0.10  0.01  0.08  0.09  0.11  0.04  0.13  0.07  0.02  0.08  0.01
order k (g/mg 0.261  0.296  0.298  0.301  0.263  0.308  0.312  0.315  0.267  0.315  0.316  0.319 
min) 0.03 0.01 0.02 0.06 0.14 0.07 0.05 0.15 0.03 0.01 0.03 0.11
h (mg/g 18.035 23.084 23.086 23.089 19.325 24.691 24.693 24.698 20.945 26.843 26.847 26.849
min)  0.01  0.07  0.09  0.02  0.09  0.01  0.15  0.03  0.11  0.06  0.05  0.01
r 0.983  0.993  0.994  0.995  0.989  0.996  0.997  0.998  0.999  0.999  0.999  0.999 
0.16 0.07 0.03 0.16 0.01 0.02 0.15 0.19 0.16 0.10 0.02 0.10
sd 0.013  0.073  0.074  0.077  0.016  0.082  0.083  0.086  0.019  0.083  0.089  0.091 
0.01 0.04 0.13 0.11 0.07 0.15 0.16 0.01 0.03 0.09 0.05 0.03
Particle kp (min
1) 0.056  0.081  0.083  0.085  0.059  0.091  0.093  0.094  0.061  0.096  0.098  0.099 
diffusion 0.01 0.09 0.03 0.07 0.13 0.02 0.05 0.05 0.03 0.02 0.13 0.01
r 0.837  0.882  0.884  0.885  0.845  0.891  0.895  0.899  0.849  0.901  0.902  0.903 
0.16 0.03 0.01 0.02 0.06 0.13 0.01 0.03 0.05 0.03 0.19 0.03
sd 0.537  0.561  0.563  0.564  0.539  0.565  0.567  0.569  0.544  0.570  0.572  0.573 
0.02 0.11 0.04 0.05 0.10 0.12 0.03 0.05 0.12 0.03 0.05 0.14
Intraparticle ki (m/g 0.113  1.972  1.976  1.979  0.117  1.983  1.986  1.989  0.120  1.996  1.997  1.998 
diffusion min0.5) 0.04 0.10 0.09 0.15 0.08 0.01 0.03 0.08 0.01 0.16 0.01 0.03
r 0.993  0.996  0.998  0.999  0.996  0.999  0.999  0.998  0.998  0.999  0.999  0.999 
0.01 0.13 0.04 0.04 0.19 0.01 0.09 0.07 0.03 0.01 0.03 0.05
sd 0.167  0.178  0.180  0.182  0.170  0.191  0.192  0.193  0.174  0.206  0.208  0.210 
0.06 0.03 0.01 0.11 0.02 0.09 0.01 0.08 0.13 0.01 0.06 0.04

3.11. Field water treatment studies 3.12. Reusable of LTA MOFs

The rural village in Dindigul district of Tamilnadu is Ammapatti To reduce the economic cost of the synthesized LTA MOFs in the
which consists of the highly eutrophicated pool lands hence the NO
3 and adsorption system, the regeneration test was performed [58]. As per the
PO3

4 ions may largely presented in the water lands may often affects the literature, the recycle of LTA MOFs was performed under the strong base
water system and also leads to the health risk for people. Hence, this namely NaOH [59]. The exhausted LTA MOFs was added with 50 mL of
study was developed by treating the LTA MOFs with the collected waste- NaOH upto 1 h and the final filtrate concentration was analyzed in
water sample. At first, the initial NO
3

3 /PO4 concentration in the water UV–Vis spectrophotometer. After that the OH
ions loaded LTA MOFs
was found to be 29.013  0.01 and 36.412  0.02 mg/L whereas the final was slightly rinsed in 50 mL of HCl, dried and followed by use for NO
3
concentration was noted to be below the tolerance limit. It was inter- and PO3
4 adsorption studies. This was performed repeatedly for several
esting to note that the synthesized LTA MOFs not only effectively times and the observed result was presented in Fig. 8. It was noticed that
removes NO
3

3 and PO4 under the batch water system but also potential the removal efficiency was decreased with respect to extraction cycles
towards the field water treatment as presented in Table 8. In addition, the and almost 70% was attained in almost 7 cycles. The good removal ef-
final pH of the treated water sample was close to neutral which ensured ficiency upto 7 cycles probably account for the electrostatic attraction of
the applicability of the MOFs. Moreover, TDS, hardness and Cl
contents the protonated LTA MOFs with that of NO
3

3 and PO4 ions. But the


was measured which was controlled by LTA MOFs by ensuring the po- presence of OH ions from NaOH may also occur on LTA MOFs surface
tential applicability at field environments. sites by giving the competition for NO
3

3 /PO4 adsorption. The good

Fig. 7. Removal mechanism of LTA MOFs towards NO
3

3 and PO4 retention.

9
I. Aswin Kumar et al. Journal of Solid State Chemistry 302 (2021) 122446

Table 7 4. Conclusions
Adsorption capacity evaluation of LTA MOFs with adsorbents on NO
3

3 /PO4
removal. In this study, LTA MOFs was developed for effective NO
3 and PO4
3

S.No. Name of the adsorbent Adsorption capacity (mg/ Reference adsorption from aqueous solution. The maximum SCs were noticed at
g) neutral pH and the developed LTA MOFs was selective on both NO
3/
Nitrate Phosphate PO3
2

4 adsorption except for SO4 at batch tests. The electrostatic attrac-
tion shows that the multivalent PO3
4 was preferably occupied by the
1 LTA MOFs 49.731  62.806  Present
0.05 0.02 study positively charged LTA MOFs surface compared with univalent NO
3 . The
2 Organic modified aluminum- 19.45 33.16 [44] kinetic rate of LTA MOFs was found to be pseudo-second-order along
manganese bimetal oxide with intraparticle diffusion models for both NO
3

3 /PO4 adsorption.
3 Amine functionalized bio-resin 6.48 48.73 [45] Moreover, the isotherms and thermodynamic parameters exhibited the
derived from corn stalk
4 Modified cellulose from corn 13.60 22.88 [46]
feasible adsorption system. The potential of LTA MOFs provides the
stalks promising support for industrial scale water treatment.
5 Solid carbon source/zero-valent 1.10  0.14  0.07 [47]
iron 0.1 CRediT authorship contribution statement
6 Al-modified biochar 89.58 57.49 [48]
7 FeCl
4 /Gemini-Mt composite 8.77 28.10 [49]
8 Activated carbon from Prosopis 10.99 13.55 [50] Ilango Aswin Kumar: Conceptualization, Data curation, Formal
juliflora analysis, Funding acquisition, Investigation, Methodology, Resources,
9 Mg/Al modified soybean straw 40.63 74.47 [51] Software, Writing – original draft, Writing – review & editing. Anto-
biochar nysamy Jeyaseelan: Writing – review & editing. Natrayasamy Vis-
10 Iron (III) and iminodiacetic acid – 33.70 [52]
functionalized magnetic peanut
wanathan: Conceptualization, Data curation, Formal analysis, Funding
husk acquisition, Investigation, Methodology, Resources, Software, Writing –
11 AGMGel composite (hydro) 30.29 36.75 [53] original draft, Writing – review & editing, Supervision, Validation,
13 Fe3O4@GelHT composite – 32.73 [54] Visualization. Mu. Naushad: Writing – review & editing, Funding
14 Zr@CSKN composite (hydro) 34.62 40.58 [55]
acquisition. Artur J.M. Valente: Writing – review & editing.
15 Zr@Fu MOF composite 43.97 56.41 [56]
16 La2O3AM@CS composite beads 27.84 34.91 [57]
Declaration of competing interest

Table 8 The authors declare that they have no known competing financial
Field applicability of LTA MOFs.
interests or personal relationships that could have appeared to influence
Water quality parameters Before treatment After treatment the work reported in this paper.
Initial NO

3 concentration (mg/L) 29.013  0.01 3.201  0.05
Initial PO3

4 concentration (mg/L) 36.412  0.02 1.082  0.01 Acknowledgement
pH 5.314  0.01 6.734  0.02
Cl
(mg/L) 546  0.03 296  0.04
The first author (I.Aswin Kumar) sincerely thank the Council of Sci-
Total dissolved solids (mg/L) 692  0.05 360  0.02
Total hardness (mg/L) 795  0.03 450  0.01 entific and Industrial Research (CSIR), New Delhi, India (F.No.08/
630(0006)/2019-EMR-I), for awarding Senior Research Fellowship. Mu.
Naushad is grateful to the Distinguished Scientist Fellowship Program
(DSFP-2021), King Saud University, Riyadh, Saudi Arabia for the finan-
cial support.

References

[1] X. Cui, H. Li, Z. Yao, Y. Shen, Z. He, X. Yang, H.Y. Ng, C.H. Wang, Removal of nitrate
and phosphate by chitosan composited beads derived from crude oil refinery waste:
sorption and cost-benefit analysis, J. Clean. Prod. 207 (2019) 846–856.
[2] M. Ward, R. Jones, J. Brender, T. de Kok, P. Weyer, B. Nolan, C. Villanueva, S. van
Breda, Drinking water nitrate and human health: an updated review, Int. J. Environ.
Res. Publ. Health 15 (2018) 1557.
[3] J. Pan, B. Gao, W. Song, X. Xu, B. Jin, Q. Yue, Column adsorption and regeneration
study of magnetic biopolymer resin for perchlorate removal in presence of nitrate
and phosphate, J. Clean. Prod. 213 (2019) 762–775.
[4] J. Castaneda-Diaz, T. Pavon-Silva, E. Gutierrez-Segura, A. Colin-Cruz,
Electrocoagulation-adsorption to remove anionic and cationic dyes from aqueous
solution by PV-energy, J. Chem. 2017 (2017) 14.
[5] K.C. Khulbe, T. Matsuura, Removal of heavy metals and pollutants by membrane
adsorption, Appl. Water Sci. 8 (2018) 19.
[6] Y. Ye, Y. Ren, J. Zhu, J. Wang, B. Li, Removal of nitrate and Cr(VI) from drinking
water by a macroporous anion exchange resin, Desal. Water Treat. 57 (55) (2016)
26427–26439.
[7] I. Aswin Kumar, M. Naushad, T. Ahamad, N. Viswanathan, Development of
triaminotriazine functionalized graphene oxide capped chitosan porous composite
beads for nutrients remediation towards water purification, Int. J. Biol. Macromol.
Fig. 8. Regeneration of LTA MOFs on NO
3

3 and PO4 adsorption studies.
170 (2021) 13–23.
[8] Y. Lu, W. Zhang, Y. Li, C. Zhang, L. Wang, L. Niu, H. Zhang, Microbial community
shift via black carbon: insight into biological nitrogen removal from microbial
removal efficiency of LTA MOFs upto 7 cycles declares the highly reus- assemblage and functional patterns, Environ. Res. 192 (2021) 110266.
able and efficient nature for adsorption studies. Moreover, the leaching of [9] P. Karthikeyan, S. Meenakshi, Synthesis and characterization of Zn-Al LDHs/
activated carbon composite and its adsorption properties for phosphate and nitrate
La3þ of LTA MOFs was investigated using an atomic absorption spec- ions in aqueous medium, J. Mol. Liq. 296 (2019) 111766.
trophotometer (AAS) and no leaching was found which explore the sta- [10] N. Viswanathan, C. Sairam Sundaram, S. Meenakshi, Sorption behavior of fluoride
bility of LTA MOFs towards adsorption studies. on carboxylated cross-linked chitosan beads, Colloids Surf. B Biointerfaces 68
(2009) 48–54.

10
I. Aswin Kumar et al. Journal of Solid State Chemistry 302 (2021) 122446

[11] L. Wang, H. Xu, J. Gao, J. Yao, Q. Zhang, Recent progress in metal-organic [35] H.M.F. Freundlich, Over the adsorption in solution, Z. Phys. Chem. 57 (1906)
frameworks-based hydrogels and aerogels and their applications, Coord. Chem. 385–470.
Rev. 398 (2019) 213016. [36] I. Langmuir, The constitution and fundamental properties of solids and liquids,
[12] C. Li, H. Xu, J. Gao, W. Du, L. Shangguan, X. Zhang, Rui-Biao, L.H. Wu, W. Zhou, J. Am. Chem. Soc. 38 (1916) 2221–2295.
X. Liu, J. Yao, B. Chen, Tunable titanium metal-organic frameworks with infinite 1D [37] M.M. Dubinin, E.D. Zaverina, L.V. Radushkevich, Sorption and structure of active
Ti–O rods for efficient visible-light-driven photocatalytic H2 evolution, J. Mater. carbons, J. Phys. Chem. 21 (1947) 1351–1362.
Chem. 7 (2019) 11928–11933. [38] A.A. Khan, R.P. Singh, Adsorption thermodynamics of carbofuran on Sn(IV)
[13] Z. Lv, Q. Fan, Y. Xie, Z. Chen, A. Alsaedi, T. Hayat, X. Wang, C. Chen, MOFs derived arsenosilicate in Hþ, Naþ and Ca2þ forms, Colloids Surf., A 24 (1987) 33–42.
magnetic chestnut shell-like hollow sphere NiO/Ni@C composites and their [39] M.R. Awual, M.M. Hasan, A. Shahat, M. Naushad, H. Shiwaku, T. Yaita,
removal performance for arsenic(V), Chem. Eng. J. 362 (2019) 413–421. Investigation of ligand immobilized nano-composite adsorbent for efficient
[14] C.H. Wang, J. Kim, J. Tang, J. Na, Y.M. Kang, M. Kim, H. Lim, Y. Bando, J.S. Li, cerium(III) detection and recovery, Chem. Eng. J. 265 (2015) 210–218.
Y. Yamauchi, Large-scale synthesis of MOF-derived superporous carbon aerogels [40] R. Saad, K. Belkacemi, S. Hamoudi, Adsorption of phosphate and nitrate anions on
with extraordinary adsorption capacity for organic solvents, Angew. Chem. Int. Ed. ammonium-functionalized MCM-48: effects of experimental conditions, 311,
59 (2020) 2066–2070. J. Colloid Interface Sci. (2007) 375–381.
[15] S. Salehi, S. Mandegarzad, M. Anbia, Preparation and characterization of metal [41] M. Naushad, Z.A. ALOthman, M.R. Awual, M.M. Alam, G.E. Eldesoky, Application
organic framework-derived nanoporous carbons for highly efficient removal of kinetics, isotherms, and thermodynamic studies for the adsorption of Pb2þ and Hg2
þ
vanadium from aqueous solution, J. Alloys Compd. 812 (2020) 152051. metal ions from aqueous medium using Ti(IV) iodovanadate cation exchanger,
[16] Q. Huo, J.S. Li, X.R. Qi, G.Q. Liu, X.B. Zhang, B.Y. Zhang, Y. Ning, Y.F. Fu, Ionics 21 (2015) 2237–2245.
J.M.S. Liu, Cu, Zn-embedded MOF-derived bimetallic porous carbon for adsorption [42] G. Sharma, B. Thakur, M. Naushad, A. Kumar, F.J. Stadler, S.M. Alfadul, G.T. Mola,
desulfurization, Chem. Eng. J. 378 (2019) 122106. Applications of nanocomposite hydrogels for biomedical engineering and
[17] W. Xiao-Kun, J. Liu, L. Zhang, D. Long-Zhang, L. Shun-Li, K. Yu-He, L. Dong-Sheng, envirmental protection, Environ. Chem. Lett. 16 (2018) 113–146.
L. Ya-Qian, Monometallic catalytic models hosted in stable metal-organic [43] M. Ganesh, P. Hemalatha, M.M. Peng, W.S. Cha, H.T. Jang, Zr-fumarate MOF a
frameworks for Tunable CO2 photoreduction, ACS Catal. 9 (3) (2019) 1726–1732. novel CO2 adsorbing material: synthesis and characterization, Aerosol Air Qual.
[18] S.J. Yang, J.H. Im, T. Kim, K. Lee, C.R. Park, MOF-derived ZnO and ZnO@C Res. 14 (2014) 605–1612.
composites with high photocatalytic activity and adsorption capacity, J. Hazard [44] K. Wu, Y. Li, T. Liu, Q. Huang, S. Yang, W. Wang, P. Jin, The simultaneous
Mater. 186 (2011) 376–382. adsorption of nitrate and phosphate by an organic-modified aluminum-manganese
[19] D. Huang, X. Wu, J. Tian, X. Wang, Z. Zhou, D. Li, Assembling of a novel 3D Ag(I)- bimetal oxide: adsorption properties and mechanisms, Appl. Surf. Sci. 478 (2019)
MOFs with mixed ligands tactics: syntheses, crystal structure and catalytic 539–551.
degradation of nitrophenol, Chin. Chem. Lett. 29 (6) (2018) 845–848. [45] J. Pan, B. Gao, W. Song, X. Xu, B. Jin, Q. Yue, Column adsorption and regeneration
[20] H.A.M. Saleh, M.I. Khalil, M.A. Qasem, M. Shahid, M.N. Akhtar, M.A. AlDamen, study of magnetic biopolymer resin for perchlorate removal in presence of nitrate
M. Ahmad, A two dimensional Co(II) metal-organic framework with bey topology and phosphate, J. Clean. Prod. 213 (2019) 762–775.
for excellent dye adsorption and separation: exploring kinetics and mechanism of [46] C. Fan, Y. Zhang, Adsorption isotherms, kinetics and thermodynamics of nitrate and
adsorption, Inorg. Chim. Acta. 512 (2020) 119900. phosphate in binary systems on a novel adsorbent derived from corn stalks,
[21] U. Yang, J. Qin, Z. Guo, Y. Hu, X. Zhang, Zn-based metal organic framework J. Geochem. Explor. 188 (2018) 95–100.
derivative with uniform metal sites and hierarchical pores for efficient adsorption of [47] H. Sun, Q. Zhou, L. Zhao, W. Wu, Enhanced simultaneous removal of nitrate and
formaldehyde, Chin. Chem. Lett. 32 (5) (2020) 1819–1822. phosphate using novel solid carbon source/zero-valent iron composite, J. Clean.
[22] J.J. He, Y.H. Xu, W. Wang, B. Hu, Z.J. Wang, X. Yang, Y. Wang, L.W. Yang, Ce(III) Prod. 289 (2021) 125757.
nanocomposites by partial thermal decomposition of Ce-MOF for effective [48] Q. Yin, H. Ren, R. Wang, Z. Zhao, Evaluation of nitrate and phosphate adsorption on
phosphate adsorption in a wide pH range, Chem. Eng. J. 379 (2020) 122431. Al-modified biochar: influence of Al content, Sci. Total Environ. 631–632 (2018)
[23] A. Jeyaseelan, N. Viswanathan, Facile synthesis of tunable rare earth based metal 895–903.
organic frameworks for enhanced fluoride retention, J. Mol. Liq. 326 (2021) [49] W. Luo, Q. Huang, P. Zeng, C. Cheng, X. Yuan, T. Xiao, M. Zhang, P. Antwi, J. Xing,
115163. S. Ren, Gemini surfactant-modified montmorillonite with tetrachloroferrate (FeCl-4)
[24] M.V. Lopez-Ramon, F. Stoeckli, C. Moreno-Castilla, F. Carrasco-Marin, On the as a counterion simultaneously sequesters nitrate and phosphate from aqueous
characterization of the acidic and basic surface sites on carbons by various solution, J. Hazard Mater. 409 (2021) 124829.
techniques, Carbon 37 (1999) 1215–1221. [50] S.V. Manjunath, M. Kumar, Evaluation of single-component and multi-component
[25] APHA, Standard Methods for the Examination of Water and Wastewater, American adsorption of metronidazole, phosphate and nitrate on activated carbon from
Public Health Association, Washington, DC, 2005. Prosopıs julıflora, Chem. Eng. J. 346 (2018) 525–534.
[26] A. Jeyaseelan, N. Viswanathan, Design of amino-functionalized benzene-1,4- [51] Q. Yin, R. Wang, Z. Zhao, Application of Mg-Al modified biochar for simultaneous
dicarboxylic acid-fabricated lanthanum-based metal–organic frameworks for removal of ammonium, nitrate, and phosphate from eutrophic water, J. Clean.
defluoridation of water, J. Chem. Eng. Data 65 (2020) 5328–5340. Prod. 176 (2018) 230–240.
[27] S. Rojas-Buzo, P. Garcia-Garcia, A. Corma, Zr-MOF-808@MCM-41 catalyzed [52] A.A. Aryee, F.M. Mpatani, X. Zhang, A.N. Kani, E. Dovi, R. Han, Z. Li, L. Qu, Iron
phosgene free synthesis of polyurethane precursors, Catal. Sci. Technol. 9 (2019) (III) and iminodiacetic acid functionalized magnetic peanut husk for the removal of
146–156. phosphate from solution: characterization, kinetic and equilibrium studies, J. Clean.
[28] J. Xu, J. Liu, Z. Li, X. Wang, Y. Xu, S. Chen, Z. Wang, Optimized synthesis of Zr(IV) Prod. 268 (2020) 122191.
metal organic frameworks (MOFs-808) for efficient hydrogen storage, New J. [53] I. Aswin Kumar, N. Viswanathan, Hydrothermal fabrication of amine-grafted
Chem. 43 (2019) 4092–4099. magnetic gelatin hybrid composite for effective adsorption of nitrate and
[29] B.J. Zhu, X.Y. Yu, Y. Jia, F.M. Peng, B. Sun, M.Y. Zhang, T. Luo, J.H. Liu, X.J. Huang, phosphate, Ind. Eng. Chem. Res. 58 (47) (2019) 21521–21530.
Iron and 1, 3, 5-benzenetricarboxylic metal organic coordination polymers [54] I. Aswin Kumar, N. Viswanathan, A facile synthesis of magnetic particles sprayed
prepared by solvothermal method and their application in efficient As(V) removal gelatin embedded hydrotalcite composite for effective phosphate sorption,
from aqueous solutions, J. Phys. Chem. C 116 (2012) 8601–8607. J. Environ. Chem. Eng. 6 (1) (2018a) 208–217.
[30] R. Mukhopadhyay, T. Adhikari, B. Sarkar, A. Barman, R. Paul, A.K. Patra, [55] I. Aswin Kumar, N. Viswanathan, Hydrothermal Fabrication of zirconium
P.C. Sharma, P. Kumar, Fe-exchanged nano-bentonite outperforms Fe3O4 oxyhydroxide capped chitosan/kaolin framework for highly selective nitrate and
nanoparticles in removing nitrate and bicarbonate from wastewater, J. Hazard phosphate retention, Ind. Eng. Chem. Res. 57 (43) (2018b) 14470–14481.
Mater. 376 (2019) 141–152. [56] I. Aswin Kumar, M. Naushad, T. Ahamad, N. Viswanathan, Facile fabrication of
[31] A. Sowmya, S. Meenakshi, A novel quaternized chitosan- melamine-glutaraldehyde tunable porous zirconium fumarate based metal organic frameworks in the
resin for the removal of nitrate and phosphate anions, Int. J. Biol. Macromol. 64 retention of nutrients from water, Environ. Sci.: Water Res. Technol. 6 (2020)
(2014) 224–232. 2856–2870.
[32] Y. Gao, C. Chen, X. Tan, H. Xu, K. Zhu, Polyaniline-modified 3D-flower-like [57] I. Aswin Kumar, C. Jeyaprabha, S. Meenakshi, N. Viswanathan, Hydrothermal
molybdenum disulfide composite for efficient adsorption/photocatalytic reduction encapsulation of lanthanum oxide derived Aegle marmelos admixed chitosan bead
of Cr(VI), J. Colloid Interface Sci. 476 (2016) 62–70. system for nitrate and phosphate retention, Int. J. Biol. Macromol. 130 (2019)
[33] M. Naushad, S. Vasudevan, G. Sharma, A. Kumar, Z.A. ALOthman, Adsorption 527–535.
kinetics, isotherms, and thermodynamic studies for Hg2þ adsorption from aqueous [58] W. Ren, J. Gao, C. Lei, Y. Xie, Y. Cai, Q. Ni, J. Yao, Recyclable metal-organic
medium using alizarin red-S-loaded amberlite IRA-400 resin, Desalin. Water Treat. framework/cellulose aerogels for activating peroxymonosulfate to degrade organic
57 (39) (2016) 18551–18559. pollutants, Chem. Eng. J. 349 (2018) 766–774.
[34] K. Pandi, N. Viswanathan, In situ fabrication of magnetic iron oxide over nano- [59] H. Wang, X. Xu, Z. Ren, B. Gao, Removal of Phosphate and Chromium(VI) from
hydroxyapatite gelatin eco-polymeric composite for defluoridation studies, liquids by amine-crosslinked nano-Fe3O4 biosorbent derived from corn straw, RSC
J. Chem. Eng. Data 61 (2016) 571–578. Adv. 6 (2016) 47237–47248.

11