1

REPORT ON

Introduction to Hybrid Materials based on Tetravalent

Metal Acid salts and their applications as ion exchangers for
metal removal from aqueous solution
BY

AKASH BONTHU
I19CY006
Under the guidance of

Prof. Dr. Kalpana Maheria

DEPARTMENT OF CHEMISTRY

SARDAR VALLABHBHAI NATIONAL INSTITUTE OF TECHNOLOGY

CERTIFICATE
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This is to certify that AKASH BONTHU, I19CY006, a Five – year Integrated

Master of Science student from Department of Chemistry, Sardar Vallabhbhai
National Institute of Technology, Surat, India has successfully completed the project
titled “Introduction to hybrid materials based on Tetravalent metal acid salts
and their applications as a Ion Exchangers for metal removal from aqueous
solution” during the academic year 2023-2024 under the supervision of Dr.
Kalpana Maheria Department of Chemistry, Sardar Vallabhbhai National Institute
of Technology for the fulfillment of the requirements of the course Dissertation
Preliminaries with Subject code CY –503 during the Ninth Semester of his Study

Project Supervisor Head of the Department

Dr. Kalpana Maheria Dr. Suban K Sahoo
Associate Professor Associate Professor
DoC DoC
SVNIT, Surat, Gujarat, India Surat, Gujarat, India
Email
kcm@chem.svnit.ac.in Email:hod@chem.svnit.ac.in

CONTENTS
Sr. No Title Page No
1. Introduction

2. Heavy Metals

3. Removal Methods of Heavy Metals

3.1. Physico – Chemical Methods
 3

3.2. Chemical Precipitation

3.3. Coagulation and Flocculation

3.4. Ion Exchange.

3.5. Heavy Metals in Food and Water

4. Tetravalent Metal Acid Salts

4.1. Structural and Transport Properties

4.2. Ion Exchange membranes

5. Synthesis of Ti – ATMP

6. Results and Discussions

7. Conclusion

INTRODUCTION

The presence of heavy metals in wastewater has been increasing with the growth of industry and
human activities, e.g., plating and electroplating industry, batteries, pesticides, mining industry,
rayon industry, metal rinse processes, tanning industry, fluidized bed bioreactors, textile industry,
metal smelting, petrochemicals, paper manufacturing, and electrolysis applications. The heavy
metal contaminated wastewater finds its way into the environment, threatening human health and
the ecosystem. The heavy metals are non-biodegradable1 and could be carcinogenic; thus, the
presence of these metals in water by improper amounts could result in critical health issues to
living organisms.

The most popular heavy metals are lead (Pb), zinc (Zn), mercury (Hg), nickel (Ni), cadmium (Cd),
copper (Cu), chromium (Cr), and arsenic (As). Although these heavy metals can be detected in
traces, they are still hazardous. Table 1 summarizes some heavy metals, focusing on their major
sources, health effects, and the permitted quantity in drinking water. The metals and others such
 4

as silver (Ag), iron (Fe), manganese (Mn), molybdenum (Mo), boron (B), calcium (Ca), antimony
(Sb), cobalt (Co), etc. are commonly available in wastewater and need to be removed.

Recent studies have focused on a particular method for heavy metal ions removal, such as
electrocoagulation (EC), adsorption using synthetic and natural adsorbents, magnetic field
implementation, advanced oxidation processes, membranes, etc. These studies stood on the
advantages and disadvantages of a specific method for wastewater treatment, including heavy
metal removal. A complete picture of the heavy metals removal methods from wastewater
resources has not been drawn yet. Therefore, the present review comprehensively and critically
discusses the available technologies to expel heavy metal ions from wastewater efficiently.
Moreover, it is essential to choose the most applicable method based on the removal efficiency,
chemicals added/adsorbents, initial concentration, optimal treated pH value, and other operating
conditions.

The methods discussed in this review are classified into adsorption-, membrane-, chemical-,
electric-, and photocatalytic-based treatments. An assessment for each method is conducted.
Additional details about the operating conditions, removal efficiency, and important remarks of
each method are listed for the reported studies in the literature in the accompanying Supplementary
Information file. Literature research is selected based on the availability of the operating and
performance parameters for each method.

Removal of heavy metal ions from wastewater is of prime importance for a clean environment and
human health. Different reported methods were devoted to heavy metal ions removal from various
wastewater sources. These methods could be classified into adsorption, membrane, chemical,
electric, and photocatalytic-based treatments. This paper comprehensively and critically reviews
and discusses these methods in terms of used agents/adsorbents, removal efficiency, operating
conditions, and the pros and cons of each method. Besides, the key findings of the previous studies
reported in the literature are summarized. Generally, it is noticed that most of the recent studies
have focused on adsorption techniques. The major obstacles of the adsorption methods are the
ability to remove different ion types concurrently, high retention time, and cycling stability of
adsorbents. Even though the chemical and membrane methods are practical, the large-volume
sludge formation and post-treatment requirements are vital issues that need to be solved for
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chemical techniques. Fouling and scaling inhibition could lead to further improvement in
membrane separation. However, pre-treatment and periodic cleaning of membranes incur
additional costs. Electrical-based methods were also reported to be efficient; however, industrial-
scale separation is needed in addition to tackling the issue of large-volume sludge formation.
Electric- and photocatalytic-based methods are still less mature.

2.HEAVY METALS
“Heavy metals” are natural elements characterized by their rather high atomic mass and their high
density. Although typically occurring in rather low concentration, they can be found all through
the crust of our planet. Commonly, a density of at least 5 g cm−3 is used to define a heavy metal
and to differentiate it from other, “light” metals. Other, broader definitions for “heavy metals”
require an atomic mass higher than 23 or an atomic number exceeding 20; these definitions are
highly error prone and confusing. Both alternative definitions cause the inclusion even of
nonmetals; resorting to the atomic mass criterion, the maximum number of elements classified as
“heavy metals” rockets high to 99 out of the in total 118 building blocks of our universe. Looking
at the periodic table of elements, we learn that heavy metals sensu stricto (according to the density
criterion) occupy the lion’s share, namely, columns 3–16, of the periods 4 to 6, encompassing the
transition metals, post-transition metals, and lanthanides.

Some heavy metals like copper, selenium, or zinc are essential trace elements, with functions
indispensable for various biological processes also driving the entire human metabolism. The
heavy metal cobalt, acting as the central atom in the vitamin B12 complex, is a key player in the
reductive branch of the propionic acid fermentation pathway; without this special heavy metal
compound, the gourmet would have to do without the unique flavor of Emmentaler cheese. Many
heavy metals are of outstanding technological significance, e.g., iron, zinc, tin, lead, copper,
tungsten, etc. Recently, different heavy metals act as the central atom of artificially designed
“bioinorganic” catalysts for special chemical transformations. Moreover, among them we find
precious noble elements like gold, silver, iridium, rhodium, or platinum. On the other hand, many
 6

of them, e.g., mercury, cadmium, arsenic, chromium, thallium, lead, and others, classically
represent the “dark side of chemistry”; they exert toxic effects already at low concentration.

Heavy metals were literally heavens sent by originating from asteroid impacts. Typically, heavy
metals occur in the earth’s crust in rather low concentrations between the low ppb ranges (noble
metals) and up to 5% (iron); here, heavy metals are mainly found chemically bound in carbonate,
sulfate, oxide, or silicate rocks or also occur in their metallic, elemental form. Weathering and
erosion resulted in their leaching and mitigation into soil, rivers, and groundwater. About 4–5
billion (about 158 and a half years) years ago, when Earth’s mantle was still liquid, heavy metals
sank to Earth’s center and formed Earth’s core, which today predominately consists of the heavy
metals iron and nickel.

2.1 HEAVY METAL REMOVAL METHODS

A. Physico-chemical methods
The following methods have been used by various researchers for removal of heavy metals.
Physical separation techniques are primarily applicable to particulate forms of metals, discrete
particles or metal-bearing particles. Physical separation consists of mechanical screening,
hydrodynamic classification, gravity concentration, flotation, magnetic separation, electrostatic
separation, and attrition scrubbing. The efficiency of physical separation depends on various soil
characteristics such as particle size distribution, particulate shape, clay content, moisture content,
humic content, heterogeneity of soil matrix, density between soil matrix and metal contaminants,
magnetic properties, and hydrophobic properties of particle surface, The conventional chemical
processes for removing heavy metals from wastewater include many processes such as chemical
precipitation, flotation adsorption, ion exchange, and electrochemical deposition. Factors that may
limit the applicability and effectiveness of the chemical process is high content of clay/silt, humic,
calcite, Fe & Ca, heavy metals, anions, or high buffering capacity.
B. Chemical Precipitation
Chemical precipitation is one of the most widely used for heavy metal removal from inorganic
effluent in industry due to its simple operation. These conventional chemical precipitation
 7

processes produce insoluble precipitates of heavy metals such as hydroxide, sulfide, carbonate and
phosphate. The mechanism of this process is based on producing insoluble metal precipitation by
reacting dissolved metals in the solution and precipitant. In the precipitation process very fine
particles are generated, and chemical precipitants, coagulants, and flocculation processes are used
to increase their particle size to remove them as sludge. Once the metals precipitate and form
solids, they can easily be removed, and low metal concentrations can be discharged. Removal
percentage of metal ions in the solution may be improved to optimum by changing major
parameters such as pH, temperature initial concentration, charge of the ions etc. The precipitation
technique is hydroxide treatment due to its relative simplicity, low cost of precipitant (lime), and
ease of automatic pH control. The solubilities of the various Metal hydroxides are minimized for
pH in the range of8.0 to 11.0.

C. Coagulation and Flocculation

The coagulation-flocculation mechanism is based on zeta potential (ζ) measurement as the criteria
to define the electrostatic interaction between pollutants and coagulant-flocculant agents.
Coagulation process reduces the net surface charge of the colloidal particles to stabilize by
electrostatic repulsion process. Flocculation process continually increases the particle size to
discrete particles through
additional collisions and interaction with inorganic polymers formed by the organic polymers
added. Once discrete particles are flocculated into larger particles, they can be removed or
separated by filtration, straining or floatation. Production of sludge, application of chemicals and
transfer of toxic compounds into solid phase are the main drawbacks of this process.

4.Ion Exchange
Ion exchangers are solid materials or liquid solutions which can take up (or absorb) positively or
negatively charged ions from aqueous electrolyte solutions and at the same time-release other ions
of equivalent amount into the aqueous solution. According to the electric charge of the ions taking
part in the ion exchange process, one can speak about cation and anion exchangers. Ion exchangers
which are able to interact with both types of ions are called amphoteric.

The ideal ion exchange process proceeds stoichiometrically, i.e., the ratio of the ions exchanged
between the two phases is strictly determined by their charges. A clear distinction can be made
between ion exchange and adsorption or liquid–liquid extraction processes, in which molecules
 8

are transferred from the aqueous phase into the solid, or organic solvent phase, without releasing
any other species into the aqueous solution.

Ion-exchange processes are important in biological systems of living organisms. They are
important not only from the point of view of selective secretion of some biological substances, but
also in the transport mechanism of certain ions crossing cell membranes, and in the signal
expansions in nerve systems.

Ion exchange processes have importance also in agriculture, because the ion-exchange properties
of the natural silicates present in the soils highly influence the composition of the interstitial liquid
available for the feeding of the plants.

Synthetic ion exchangers have proved to be very useful tools both in industry and in the laboratory,
because by means of ion exchangers the concentration of certain ions in solution can be changed
very easily without unwanted disturbances of the total composition of the electrolyte, and selective
separations, extractions, and enrichment procedures can be carried out with them.

Ion exchangers can be divided into cation exchangers and anion exchangers, with a further division
into strong and weak ones according to the functional groups. The choice between a cation and
anion exchanger will depend upon the net charge of the analyte under the conditions used – anion
exchange for negatively charged analytes and cation exchange for positively charged ones.
Whether to use a strong or weak exchanger is a more difficult decision. The charge density of a
strong ion exchanger is essentially independent of pH, but for a weak ion exchanger it is dependent
upon the pKa of the stationary phase. Ion exchange chromatography is carried out normally with
an aqueous mobile phase (buffer) and tends to preserve biological activity to a high extent. Elution
in IEC is accomplished by changing the pH or – most commonly – by increasing the ionic strength
of the mobile phase.

In analytical biotechnology IEC is used for process monitoring (amino acids, sugars, certain media
compounds and products) and for quality control purposes, for example, for determination of
glycosylation variants or detection of deamidated product molecules (proteins). In addition, IEC
type stationary phases are also used in many sample preparation schemes for rapid enrichment of
the target molecule-containing fraction prior to further analysis.
 9

While being a most powerful and widely used preparative separation technique, analytical IEC has
the disadvantage of being difficult to couple to MS due to the need for a high salt elution buffer.
For the same reason, miniaturization is difficult since high salt buffers are intrinsically unsuited
for electro chromatographic applications, i.e., chromatographic separation, where the electro-
osmotic flow is used to drive the mobile phase. Pressure-driven μ-LC is possible in the IEC mode
but is more difficult to performVie
 10

Fig (1). Removal of heavy metal ions by ion exchange process. (2) Conventional methods for the removal of
heavy metal ions.
 11

2.2 Heavy Metals in Food and Water

There are many ways heavy metals can enter the environment and agriculture. Heavy metal
contamination of foods originates by weathering of the bedrock, air pollution directly, as well as
soil irrigation with polluted waters and polluting groundwater. Environmental contamination,
primarily by industrial and human activity, refers to soil or groundwater that are the most common
access routes of heavy metals such as lead, mercury, chromium, arsenic and cadmium. Reports
have shown that increased amounts of heavy metals in the human daily diet are related to region,
available food products and industry. Occasionally, a metal is not released into the environment,
but human industrial activities result in exposure to those which are naturally occurring. For
example, in the vicinity of a mine, soil contamination can be observed, which can result in the
presence of heavy metals in local crops. Certain regions and related industries are known to be
specific for the emergence of these heavy metals in high concentrations, i.e., in China, areas
surrounding coal-fired power plants are polluted by mercury up to 10 times more than the average
soil sample 55 km away from these places .

Mercury has a significant influence on the human body. Reports have shown that mercury is
largely ingested through the consumption of fish: marine, freshwater and starfish. A study
conducted in China revealed that mercury levels in children’s blood varies depending on the region
and on the rate of fish consumption. The level of organic mercury (e.g., methylmercury) depends
on the species of fish. The bio accessibility of mercury in food differs between raw and cooked
foods and can be reduced by drinking green or black tea and black coffee during a meal, which
can be correlated to the presence of phytates and tannins. The presence of mercury has also been
confirmed in lettuce, water spinach, amaranth, rice, etc. Li et al. examined the impact of coal-fired
power plants on vegetables and crops and showed that mercury pollution is more prominent in
leaves than roots.

However, absorption of mercury in the gastrointestinal track is approximately 7% to 15%,

compared with 80% when inhaled. This comparison shows that inhaling mercury vapors, which
occurs, e.g., during small-scale gold mining, silver-ore work and dental work with amalgams, is
 12

dangerous. Mercury causes neurological problems and impairs kidney function. Additionally, a
correlation has been determined between infertility and higher blood mercury levels.

Lead is another heavy metal which has an important impact on human health. Human poisoning
is often associated with lead gasoline, mining and battery recycling, but the source of the poisoning
may be unexpected in terms of wall paints or binders in sewer pipes. In the Middle East, especially
Egyptian villages, inhabitants produce household flour (the main component of their diet) using a
stone mill, however, the stone is held with a lead binder, which causes contamination. Lead and
cadmium cause the loss of calcium and abnormal bone metabolism, leading to osteoma Lacia
Exposure to lead is especially dangerous for children under six years of age, as it disturbs
development, growth and differentiation of nerve cells, and it causes damage of bone tissue. In the
1980s, the National Health and Nutrition Examination Survey (NHANES) indicated that an
estimated 88% of children aged 1–5 years had blood lead levels (BLLs) ≥ 10 µg/dL. Since that
time, the numbers have been rapidly decreasing. Recently, the new reference value of 3.5 µg/dL
has been recommended to the American Center for Disease Control and Prevention (CDC), based
on the 98th percentile of the 2011–2014 NHANES data. Blood-led screening programs play an
important role in reducing exposure risks, especially at the population level.

Cadmium has been found to greatly increase the risk of cardiovascular disease by smoking. Li et
al. showed the effects of cadmium in tobacco as a cardiovascular disease factor. Leafy vegetables,
oilseeds, crops, organ meat, and nuts are known to contain high levels of cadmium. In China,
cadmium is mainly ingested via consumption of rice. Furthermore, the dismantling of Chinese e-
waste exposes those in the vicinity to higher concentrations of cadmium, and those that consume
rice grown in the area display a 60% increase in hazard quotient.

Food contamination with cadmium can come from natural sources, as well as from sewage and
fertilization that gets through groundwater and runoff from fields into water bodies, causing the
presence of cadmium in fish and oysters. One third of the total Cd (II) amount in the human body
is accumulated in the liver and in the kidneys.

Due to the harmfulness of cadmium, which promotes serious health issues even after short-term
exposure, complete avoidance is recommended. The adverse effects of chronic exposure to
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cadmium ions are as follows: anemia, insomnia, kidney damage, bladder and prostate cancers, and
osteoporosis, among others.

However, unexpected ingestion of cadmium may originate from sources such as pigments and
food dyes. Additionally, studies have shown that a vegetarian diet possesses higher levels of
cadmium compared to a nonvegetarian diet. Spongin revealed that the highest ratio of cadmium is
in vegetables and plant products such as sunflower seeds, spinach and potatoes, which can exceed
100 µg/kg of cadmium.

Consumption of cadmium has a particularly negative effect on fertility, moreover, it can cause
ototoxicity and cardiovascular diseases. Furthermore, it has been shown that iron deficiencies are
associated with increased absorption of divalent metals, including cadmium, cobalt and
manganese. This condition was also confirmed in breast-fed infants, whose iron-poor diets were
associated with increased levels of lead, cobalt and cadmium.

Chromium occurs as trivalent chromium and hexavalent chromium in the environment. In food,
chromium is present in its low-toxicity trivalent form. However, in changing conditions (e.g., pH)
chromium (III) can convert to chromium (VI). Trivalent chromium is found in nuts, broccoli,
whole-grain products, and eggs. Studies have examined the impact of chromium on glucose
metabolism and fat loss. Hexavalent chromium is toxic and carcinogenic. Chromium (VI) is
primarily generated by human activity, and is used in leather tanning, chromium plates, wood
preservation, etc. Areas with tanning factories are frequently contaminated by chromium (VI)
where sewage waste affects the composition of groundwater and consequently soil. In Kanpur,
India, drinking water contains high concentrations of chromium (VI) exceeding the average by
approximately 390-fold and causes digestive, skin and ocular problems.

Arsenic is a well-known toxin and carcinogen. It can be found in the air, water and soil. Hopenhayn
et al. examined the association between consumption of arsenic in drinking water and infant birth
weight. Higher dosage of arsenic negatively affected children’s weight by approximately 57 g.
Geothermal activity in some regions promotes increased levels of arsenic.
 14

In some countries, the CCA (copper-chromium-arsenic) preservative substance has been used to
treat timber. This leads to the presence of heavy metal pollution in the soil. Hence, CCA is the
source and cause of heavy metals, such as arsenic, in food. Singh and Ghosh tested arsenic levels
in water, soil and food, where the concentration of arsenic was much higher than the WHO’s
recommended limit for drinking-water (10 μg/L). Moreover, residents of contaminated areas are
constantly exposed to cumulative effects of consumed arsenic from wheat, water and animal
products. The most common way of poisoning and intake of heavy metals is the daily consumption
of contaminated food. Studies have proven that pollution of the main dietary ingredients is the
primary cause of adverse effects. Osakwe et al. showed that residents of South-East Nigeria who
consumed vegetables and rice contaminated with high ratio of heavy metals, exceeded acceptable
limits for Pb, Ni, and Cd.

Human activities such as traffic, industry and modern agriculture are also the reasons for honey
contamination by toxic metals (particularly Ni and Cr). This situation occurs when nectar is
collected by honeybees in the flora of serpentine soils with elevated Ni content. The production of
paddy rice at serpentine sites in Taiwan has been revealed as the main source of Ni (II) exposure
for humans living there. Nickel can also be found in cocoa and chocolate. It is worth mentioning
that Ni (II) ions are important for some plant and bacterial enzymes, however, nickel pollution is
increasing in the environment. In Europe, the highest levels of nickel in vegetables were found in
Italy, nonetheless, the values found were of no concern for human or animal health. A study by
Zeinali et al. on the dietary intake of Cd, Cr, Pb, Cu, and Ni also showed that nickel content in
meat was acceptable, and the highest hazard was estimated for Pb and Cd.

Naudia and colleagues examined over 100 samples of meat, vegetables, and fish from African’s
open markets, and showed using ICP-OES and ICP-MS methods that the content of Cd, Cr, Hg,
Pb, Zn, and as exceeded WHO standards, and had a specifically negative impact on residents’
health.

Mounica et al. determined that approximately 10% of lead and 10–50% of cadmium from the
amount found in cocoa powder was bioavailable, and the concentration of these heavy metals
depended on geographical origin. Additionally, the content of heavy metals in a specific product
may depend on the production stage within a plant. In the case of maize processing, germs possess
 15

the highest concentration of heavy metals. Proper food preparation and processing are very
important in reducing heavy-metal contamination of food products. Many beverages are polluted
by heavy metals including lead, cadmium, and arsenic. Even juicing vegetables and fruits, brewing
coffee or extracting ginseng can change the heavy-metal concentration in the product

3.Tetravalent Metal acid salts

An inorganic structure is usually more stable than an organic structure towards temperature,
ionizing radiation and oxidizing agents. Thus, inorganic membranes may find practical
application, especially in those cases where organic membranes cannot be employed because of
their degradability. Furthermore, knowledge of crystalline structure gives a possibility of relating
transport properties to the arrangement of fixed charges, counter-ions and water molecules. This
paper, after a general discussion of the properties of homogeneous and heterogeneous ion
exchange membranes consisting of cerium and zirconium phosphate, reports the recent results
obtained in the preparation of pellicular zirconium phosphate and of mixed inorganic-organic
membranes having a "tailor-made" porosity

1. Structural and transport properties of acid salts of tetravalent metals and their
salt forms
Acid salts of tetravalent metals were initially obtained as amorphous materials having very easily
hydrolysable acid groups in alkaline medium. In 1964 they were also obtained as crystalline
compounds and their structure and ion-exchange properties were extensively investigated [9-10].
To date, more than twenty crystalline acid salts with general formula [M(IV)(X04) 2] H2 -
n H2 O (M(IV) = Zr, Ti, Th, Ce, etc.. and X04 = P04 or As04) have been prepared. Furthermore,
three acid salts of general formula [M(IV) 2 (X04) 3] H have been obtained recently, The acid
protons can be exchanged by an equivalent number of other cations, while several polar organic
molecules, such as amines, diamines, alcohols etc. ., can be intercalated in acid salts of
tetravalent metals having a layered structure of a or y type. An extensive literature on acid salts
 16

[14-16, summarized in recent reviews and books, is now available. However, to better
understand the methods of preparation and the properties of membranes constituted by layered
acid salts, it is very useful to give a brief account of the principal characteristics of these
compounds. Two different classes of layered acid salts are presently known, the a- and y-layered
acid salts. Some important acid salts with an a-layered structure. Among them, the zirconium
acid phosphate is certainly the most intensely investigated in various laboratories. Its layered
structure has been elucidated by Clearfield. Each layer consists of zirconium atoms lying in a
plane and bridged through phosphate groups located alternatively above and below this plane.
Three oxygen atoms of each tetrahedral phosphate are linked to three zirconium atoms, while the
fourth oxygen bears a proton which can be exchanged with other counter-ions. Thus, each layer
can be considered a planar macro anion [Zr(P04)2] ninth negative charge of which is balanced
by an equivalent a number of protons, or other cations. The layered crystal may thus be regarded
as being made up of packed macro anions with interposed counter-ions, so that the interlayer
distance depends on the size and hydration of the counter-ions [10] . Under an electric field the
counter-ions move in the interlayer spacing. The electrical specific conductance strongly depends
on the degree of crystallinity, 140 ranging from 10-2 for completely amorphous materials to 10 --
s Q - '-cm - ' for materials with very high degree of crystallinity. On the other hand, the stability
towards hydrolysis in alkaline medium is higher for crystalline than for amorphous materials.

2. Ion-exchange membranes constituted of acid salts of tetravalent metals

Heterogeneous membranes obtained using zirconium phosphate The stability of a-zirconium
phosphate towards temperature is very good. The hydration water is lost at about 100'C, while
the formation of pyrophosphate occurs at a relatively high temperature (450 ° -500° C). In salt
form (e. g. Na+ form), the exchanger is stable even at higher temperature, thus the thermal
stability of membranes containing zirconium phosphate as active material depends essentially on
the nature of the binder used. Polyvinylidene fluoride and Teflon are very good binders for
temperatures less than 200'C. For higher temperatures, inorganic binders, such as silicates, must
be employed. Some general aspects of these membranes, such as their preparation and the choice
of the binder in connection with the particular use of the membrane have already been reported
in a previous review. The concentration potentials of membranes constituted of zirconium
phosphate with differing degrees of crystallinity are shown in It can be noted that the ideal
behavior is lost at lower concentrations as the degree of crystallinity of the exchanger is
 17

increased. Resting to point out that these membranes, although being heterogeneous, behave as
homogeneous porous membranes, the pores being free spaces between adjacent microcrystals of
zirconium phosphate. This can be easily explained by remembering that, at room temperature,
the proton transport essentially occurs at the surface of the microcrystals. For this reason, the
concentration potential depends essentially on the nature of the counter-ions present on the
crystal surface. An equation which relates e.m.f. values to the ionic fraction, ACM, of a given
cation M present on the surface, has been derived. This was tested for membranes prepared with
crystals of zirconium phosphate, the surface protons of which - but not the inner ones - were
partially or totally replaced by Cs* ions. The presence of an organic binder further lowers the
already low conductance of the inorganic ion exchangers. Thus, the use of these membranes is
restricted only to those cases in which, owing to the highly drastic conditions, no other available
ion-exchange membranes can be employed.

1. SYNTHESIS OF Ti – ATMP

In this synthesis, 0.2 M of ATMP was dropwise added to 0.1 M TiCl4 (10% Sulphuric acid) at
room temperature along with continuous stirring at 400 RPM, the resultant mixture was further
stirred for an hour. Thereafter, it is kept for ageing for about 3 h and then filtered, followed by
washing with distilled water until the removal of Cl- ions. Then, it was dried at room temperature
and sieved up to 30–60 mesh size.
To convert the material into acidic form, the material was acid treated using 1 M HNO3, wherein,
5 g material is taken in 150 ml stoppered conical flask. In this flask, 1 M HNO3 solution is added
(50 ml/ gm) and kept in contact with the material for 30 mins with intermittent shaking. Then, the
material was separated from HNO3 by decantation, and washed with distilled water for removal of
adhered acid. This procedure is repeated 5 times. Finally, the material was dried at room
temperature.

Ti-ATMP has been synthesized as per reported method and various characterizations of Ti-ATMP
have been performed that include, SEM- EDX, XRD, FTIR and TGA analysis have been
performed to confirm the reproducibility of the material. The characterization data matched quite
 18

well with the reported literature. An absence of sharp peaks in XRD pattern of Ti-ATMP indicates
amorphous nature of the Ti-ATMP material.

The SEM images of Ti-ATMP show uniform morphology and granular nature of material. The
elements present in Ti-ATMP were confirmed by EDX analysis and elemental composition is
found to be, C: 18.56 wt%, O: 50.95 wt%, P: 20.08 wt% and Ti: 10.41 wt%.

RESULTS AND DISCUSSIONS

 19

By using bifunctional phosphonic acids, (HO) 2 0P-R-PO(OH)2, adjacent inorganic sheets with
the same structure of a-zirconium phosphate can be connected by organic R-radicals. Such cross-
linked or pillared zirconium phosphates, predicted by Alberti in 1974, have been recently
obtained by Dines et al. and in our laboratory. These compounds possess a permanent porosity
which may be changed within a large range by an appropriate choice of the size and length of the
R-radical. As an example, it shows a pillared zirconium phosphate with -R- = ---C, H4. The
development of such a new class of molecular sieves is important, not only in the field of the
sorbents and catalysts, but also in membrane technology. Membranes consisting of such
compounds could have interesting selective transport properties because of their filtering
properties on a molecular or ionic sieve basis. Selective separation of mixtures of molecules
having different sizes could be performed and new ion-sieve electrodes could be also obtained.
As discussed previously, the electrochemical resistance of heterogeneous membranes constituted
of an inorganic exchanger and a binder is usually high, while the perm selectivity is good only
for concentrations less than 10 - 'M. On the other hand, homogeneous membranes constituted of
pure fibrous exchangers have lower electric resistance, but their porosity is high, hence their
perm selectivity is good only for concentrations less than 10 -'M. Their use is therefore restricted
to cases in which high fluxes and low perm selectivity are required. To improve the properties of
the inorganic membranes, we are working in different directions.

CONCLUSION
Inorganic and organic-inorganic ion-exchange membranes are very attractive because of their
potential uses in many membrane technologies where organic membranes cannot be employed
because of their degradability. Many Investigations are, however, still necessary before good
inorganic membranes can be prepared on a commercial basis. Great advances have already been
made in the last few years and new possibilities will open in the future from the development of
new organic-inorganic materials. Commonly seen in rare-earth chemistry and materials science,
highly charged metal ions play key roles in many chemical processes. Computer simulations
have become an important tool for scientific research nowadays. Meaningful simulations require
reliable parameters. In the present work, we parametrized 18 M(III) and 6 M(IV) metal ions for
four new water models (OPC3, OPC, TIP3P-FB, TIP4P-FB) in conjunction with each of the 12–
 20

6 and 12–6-4 nonbonded models. Similar to what was observed previously, issues with the 12–6
model can be fixed by using the 12–6-4 model. Moreover, the four new water models showed
comparable performance or considerable improvement over the previous water models (TIP3P,
SPC/E, and TIP4PEW) in the same category (3-point or 4-point water models, respectively).
Finally, we reported a study of a metalloprotein system demonstrating the capability of the 12–6-
4 model to model metalloproteins. The reported parameters will facilitate accurate simulations of
highly charged metal ions in aqueous solution.

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Reactive Polymers, 7 (1988)221.

3.Synthesis and Characterization of a new phase of Titanium Phosphate and its application in
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4. Shah, Brijesh, and Uma Chudasama. "Synthesis and characterization of a novel hybrid
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titanium amino tris (methylene phosphonic acid) and its application as a cation exchanger."
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5.Patel, Ayushi, Dhara Morawala, Henil Kumar Lanka Pati, Brijesh Shah, and Kalpana Maheria.
"Ti-ATMP
 21

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