МАТЕРІАЛИ НА ОСНОВІ ОКСИДІВ ТИТАНУ І МАНГАНУ ДЛЯ СЕЛЕКТИВНОГО ВИЛУЧЕННЯ ЛІТІЮ З ВОДНИХ ДЖЕРЕЛ
Due to the ever-increasing production of electronic portable devices, including gadgets, lithium recovery is used to produce lithium-ion batteries. Lithium is electrochemically active, has the highest value of oxidation-reducing potential and the highest specific heat capacity among solid materials,...
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| author | Dzyazko, Yuliya Chaban, Mariya Bystryk, Olga |
| author_facet | Dzyazko, Yuliya Chaban, Mariya Bystryk, Olga |
| author_institution_txt_mv | [
{
"author": "Yuliya Dzyazko",
"institution": "V.I. Vernadskii Institute of General and Inorganic Chemistry National Academy of Sciences of Ukraine, ave. Academician Palladin, 32\/34, Kyiv, 03680, Ukraine"
},
{
"author": "Mariya Chaban",
"institution": "V. I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine, 32\/34, Academic Palladin Avenue, Kiev, 03142, Ukraine"
},
{
"author": "Olga Bystryk",
"institution": "V. I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine, 32\/34, Academic Palladin Avenue, Kiev, 03142, Ukraine"
}
] |
| author_sort | Dzyazko, Yuliya |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:40Z |
| description | Due to the ever-increasing production of electronic portable devices, including gadgets, lithium recovery is used to produce lithium-ion batteries. Lithium is electrochemically active, has the highest value of oxidation-reducing potential and the highest specific heat capacity among solid materials, making it a key element in the modern revolution of electric vehicles. The crust contains about 0.007% lithium, which is not in its pure form, but its insignificant concentrations are found in virtually all volcanic rocks and in the waters of mineral springs, sea water, and oceans. There are more than 20 minerals that contain lithium, but only few of them have content that is sufficient for commercial interest. A promising area is the processing of brines that are formed after desalination of seawater and mine waters. It is environmentally friendly and cost-effective. Since the concentration of lithium in such resources is low, sorption methods are advantageous compared to other. In this article materials that are widely studied in order to produce lithium-selective adsorbents are described. Most amphoteric oxides and hydroxides are amphoteric ion exchanges having both cation exchange and anion exchange properties. Such materials are of scientific interest in connection with the study of fission fragments behavior, release of radioactive isotopes, decontamination of sewage and concentration of microquantities of elements. The synthesis of such ion exchangers as amphoteric oxides and hydroxides is fairly simple and their cost per unit of capacity in most cases is much lower than the cost of organic resins. The combination of the material formed on the basis of hydrated titanium dioxide with known lithium manganese spinels allows to obtain a strong ion-exchange material for the selective extraction of lithium ions. |
| doi_str_mv | 10.33609/0041-6045.85.2.2019.88-100 |
| first_indexed | 2025-09-24T17:43:28Z |
| format | Article |
| fulltext |
УДК 544.726.3 doi: 10.33609/0041-6045.85.2.2019.88.2019.88-100
M.O.Chaban*, Y.S.Dzyazko, O.V.Bystryk
MATERIALS BASED ON TITANIUM AND MANGANESE OXIDES
FOR SELECTIVE RECOVERY OF LITHIUM FROM WATER SOURCES
V.I.Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences
of Ukraine, 32/34 Academic Palladin Avenue, Kyiv, 03142, Ukraine
*e-mail: mary.chaban@gmail.com
Due to the ever-increasing production of electronic portable devices, including gadgets, lithium
recovery is used to produce lithium-ion batteries. Lithium is electrochemically active, has the
highest value of oxidation-reducing potential and the highest specific heat capacity among solid
materials, making it a key element in the modern revolution of electric vehicles. The crust
contains about 0.007 % lithium, which is not in its pure form, but its insignificant concentrations
are found in virtually all volcanic rocks and in the waters of mineral springs, sea water, and
oceans. There are more than 20 minerals that contain lithium, but only few of them have
content that is sufficient for commercial interest. A promising area is the processing of brines
that are formed after desalination of seawater and mine waters. It is environmentally friendly
and cost-effective. Since the concentration of lithium in such resources is low, sorption methods
are advantageous compared to other. In this article materials that are widely studied in order
to produce lithium-selective adsorbents are described. Most amphoteric oxides and hydroxides
are amphoteric ion exchanges having both cation exchange and anion exchange properties. Such
materials are of scientific interest in connection with the study of fission fragments behavior,
release of radioactive isotopes, decontamination of sewage and concentration of microquantities
of elements. The synthesis of such ion exchangers as amphoteric oxides and hydroxides is
fairly simple and their cost per unit of capacity in most cases is much lower than the cost of
organic resins. The combination of the material formed on the basis of hydrated titanium dioxide
with known lithium manganese spinels allows to obtain a strong ion-exchange material for the
selective extraction of lithium ions.
K e y w o r d s: titanium dioxide, manganese oxide, lithium, ion-exchange material.
INTRODUCTION. The number of high-tech
and alternative energy products that are being
developed and used is steadily increasing, parti-
cularly in the fields of information, communica-
tion technologies, energy and mobility. Such
growth contributes to the demand for metals that
previously had a limited range of applications.
Most of these technological metals are geo-
chemically rare; their average mass concentration
in the earth’s crust is less than 0.01 % [1]. Becau-
se of their importance in modern technology, sci-
entists have begun to search for sources for the
extraction of such metals.
Some of the studies conducted have determi-
ned that the extraction of technological metals is
a multifactorial task, which, among other things,
depends on the environment. For example, since
mine development affects the quality of air, water
and soil, states often start protecting the environ-
ment by inhibiting the extraction of metals. Tech-
nological innovation helps meet growing needs,
but there is a point of view that negative effects
can only be delayed [2].
In order to determine how significant these
impacts are from a social point of view, it is ne-
cessary to consider in which products these me-
tals are used and which processes can provide.
Significant resource costs can be justified if the
© M.O.Chaban, Y.S.Dzyazko, O.V.Bystryk , 2019
Фізична хімія
88 ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2
mailto:mary.chaban@gmail.com
use of metal can replace the less efficient techno-
logy, with the use of which the benefits to the en-
vironment will dominate the cost of extraction.
Existing needs in lithium and perspectives
Lithium is electrochemically active, has the
highest value of oxidation-reducing potential and
the highest specific heat capacity among solid
materials, making it a key element in the modern
revolution of electric vehicles.
Energy conservation is a key factor in the use
of electric vehicles. Lithium-ion batteries are per-
ceived as traction batteries in demand for electro-
mobility. The long-term dominance of lithium bat-
tery chemistry is anticipated, which makes lithi-
um one of the most important elements for the
development of electric vehicles in both short and
long-term periods.
Lithium is only a small part of a lithium
battery: 39 grams of lithium carbonate per kilog-
ram of the final battery, equal to 12 kg of lithium
carbonate per vehicle with 300 kg of battery. The
amount of lithium needed for the production of
batteries increases by more than 20 % each year
and is projected to continue in the coming years [3].
However, the lithium market is not limited to the
production of batteries — batteries are the largest
category in lithium consumption (21 % of the mar-
ket in 2009), since they are used in electronics,
but other uses of lithium are ceramic and glass
industry (30 %), lubricants (10 %), air treatment
(5 %), metallurgy (5 %) and primary production
of aluminum (3 %) [4].
Today, 35 % of the world’s production of
lithium is used for lithium-ion batteries, and the
growth is projected to rise to 66 % by 2025. In
recent years, the volume of lithium production is
almost unchanged, and in terms of spent mate-
rials, less than one percent of lithium is recycled
for reuse [5]. The demand for lithium is increa-
sing annually by 5–7 % and will continue to grow
at the same pace for another decade. This does
not take into account the possible increase in the
production of hybrid and electric vehicles [6].
Production of lithium
The crust contains about 0.007 % lithium,
which is not in its pure form, but its insignificant
concentrations are found in virtually all volcanic
rocks and in the waters of mineral springs, sea wa-
ter, and oceans. There are more than 20 minerals
that contain lithium, but only four of them (lepido-
lite, spodumene, petalite and ambligonite) have
content that is sufficient for commercial interest.
The most important ore for the lithium industry
is spodumene (LiAlSi2O6) [7]. Most lithium is ext-
racted from brines or sea water in the form of
concentrated carbonate during warm time of the
year. Brines from the earth’s crust, called conti-
nental/subterranean brines, are the main source
of lithium carbonate production.
Active lithium extractions from natural brines
are known in Chile, Argentina, the USA and Chi-
na. All processes are based on solar evaporation
for the concentration of brine, sometimes in com-
bination with precipitators or sorbents based on
aluminum oxide for selective recovery of lithium
[8]. The largest producer of lithium materials
SQM works with brines from Salar de Atacama
in Chile, with an initial concentration of lithium
of 0.15 %. The use of "free" solar energy for eva-
poration is a very important aspect in reducing
the energy needs of the enterprise. The produc-
tivity of the production depends on the topogra-
phical conditions (average temperature, wind,
humidity) and the composition of the brine (the
initial content of lithium and other elements, in
particular, magnesium, which forms hygrosco-
pic salts and keeps a portion of lithium-contai-
ning brine) [8].
The development of ore deposits is active in
Australia, Brazil, Canada, China, Portugal, and Zim-
babwe. Lithium is found in many minerals, but
only spodumene or petalite ores are commercial-
ly interesting. Concentrates of ore containing lithi-
um oxide, are used mainly in the glass and cera-
mic industry and are not converted to lithium
carbonate, since obtaining carbonate from brines
is much cheaper [9].
The problem of producing lithium from sea-
water has been considered since 1970, when it was
assumed that thermonuclear installations would
greatly increase the demand for lithium. Due to
the positive prospects for lithium-ion batteries, the
problem has become relevant again. Sea water is
Materials based on titanium and manganese oxides for selective recovery ...
ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2 89
an attractive source of lithium, as the total lithium
content in it is about 2.4⋅1011 tons. However, the
average concentration of lithium is 0.173 mg/l,
which is approximately 10 thousand times less
than that in brines [10].
It was proposed to combine solar evapora-
tion, ion exchange and dilution of lithium chloride.
Recent studies focus on ion-exchange methods,
in particular, on adsorbents based on manganese
oxide because of its high selectivity to lithium
ions. However, for today the existence of real
factories that would use these technologies is
unknown.
With an efficiency of 20 % and a concentra-
tion of 0.173 mg/l to produce 1 kg of lithium car-
bonate, 5430 m3 of seawater must be processed.
In order to meet current needs (68500 tons in 2010)
only with sea water, it is necessary to process
3.7⋅1011 m3 of water per year.
Lithium from brines is estimated to cover on-
ly 0.49–1.37 % of the needs for lithium batteries,
while producing lithium from seawater can cover
32–82 % of the needs [8].
From the calculations made it can be conclu-
ded that the costs of lithium production will not
be overcome by the advantages of electric motors
for the environment, unless sea water is used as
a source of lithium.
Hydrated titanium dioxide
Most amphoteric oxides and hydroxides are
amphoteric ion exchanges having both cation ex-
change and anion exchange properties. Such ma-
terials are of scientific interest in connection with
the study of fission fragments behavior, release
of radioactive isotopes, decontamination of sewa-
ge from radiochemical industries, studies in the
field of radiochromatography and concentration of
microquantities of radioactive elements.
Inorganic ion exchangers have several advan-
tages over synthetic resins, since in most cases
the latter are destroyed in solutions at temperatu-
res above 150 °C, as well as unstable against ag-
gressive media and radiation, in contrast to inor-
ganic ion exchangers.
The synthesis of such ion exchangers as am-
photeric oxides and hydroxides is fairly simple and
their cost per unit of capacity in most cases is
much lower than the cost of organic resins [11].
When using inorganic ion exchangers for the
purification and decontamination of industrial so-
lutions and sewage, it is often not necessary to re-
generate ion exchanger, its one-time use is econo-
mically justified. Such inorganic ion exchangers,
which have zirconium and uranium hydroxides
(as well as zirconium phosphate), are characteri-
zed by high selectivity and allow clear separation
of elements of the same group of periodic system.
In addition to ion-exchange sorption, ampho-
teric oxides and hydroxides also have the ability to
chemical and molecular sorption.
The main disadvantage of such materials is
their low sorption capacity compared to synthetic
resins. Moreover, amphoteric oxides and hydroxi-
des are dissolved in concentrated solutions of
acids and alkalies, which makes impossible to use
them in processes with significant change in the
concentration of hydrogen ions. However, if a ion
exchanger has polymer mesh structure, it is practi-
cally stable in any range of pH.
By rational use of the anion and cation excha-
nge properties of hydroxides and oxides, specific
amount of impurities can be introduced to the sur-
face, which will have a great influence on the re-
gulation of sorption properties.
It is known that the properties of solids are
determined not only by chemical composition, but
also by the peculiarities of their structure, there-
fore, new solid phase materials can, in principle,
be created both by the use of new chemical com-
positions and by the development of new produc-
tion processes that allow alteration of structural
properties dependent on defects in electron and
crystalline structure [12].
In the study of the properties of hydrated ti-
tanium dioxide, a significant contribution of water
to it was found. When investigating such substan-
ces for the purpose of their practical use, one of
the key issues is the determination of oxygen-wa-
ter groups, as well as their quantitative ratios and
interactions with the ions.
Structure of hydrated titanium dioxide. When
systematically studying the ion exchange sorption
of cations of mono- and bivalent metals with dif-
M.O.Chaban, Y.S.Dzyazko, O.V.Bystryk
90 ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2
ferent dispersed modifications of titanium (rutile,
anatase, amorphous) it was shown that for hyd-
rated titanium dioxide three types of sorption
centers with different acidity are usual (pK1 = 6–
8, pK2 = 9.8–10.2, pK3 = 11–12), which are suc-
cessively filled with sorbed ions when the acidi-
ty of the solution decreases. The absence of the
first type of sorption centers in rutile determines
its significant difference from other modificati-
ons of hydrated titanium dioxide. The selectivity
of sorption, which is seen mainly in the first sta-
ge of exchange, is expressed in the overwhel-
ming sorption of both small (Li+) and large (K+)
and similar is size (Ba2+) cations. At the same ti-
me, ions of medium size (Na+, Ca2+, Sr2+) are
practically not adsorbed. The sorption of selective-
ly absorbed cations is activated — increasing with
increasing temperature.
These results can be explained by the follo-
wing. First, the surface of titanium dioxide is
formed by valence-unsaturated oxygen atoms.
Given that the coordination number of oxygen
in the crystalline modifications of this oxide is
equal to three, according to Poling’s rule, the un-
compensated charge of these atoms, depending on
the coordination degree from the substrate by the
titanium atoms, may vary and equal to the num-
ber of fractions of three –2/3 and –4/3 (for cases
of coordination from the matrix with two and one
titanium atoms, respectively). The hydrogen ions
neutralize the surface charge, forming on the sur-
face a functional grouping consisting of hydroxyl
and bridge groups (Ti–O(H)–Ti) [13].
Secondly, in the surface layer of the titanium
hydroxide particles, there are cavities formed by
oxygen atoms that are both valence-saturated and
unsaturated from the matrix. The size of these
atoms is discrete and is determined by the method
of packing of the cavity forming atoms (tetrahed-
ron, octahedron, cube, etc.). Various cavities may
be adjacent and separated by the oxygen atoms
that are common to them.
Thirdly, the cation sorption in the cavity can
occur without the prior dissociation of functional
groups and is energetically determined by the po-
ssibility of replacing the hydration shell of the ion
with "solvating" oxygen atoms of cavity, followed
by displacement of hydrogen ions, a process simi-
lar to the formation of surface titanates [14].
Such a structure of the hydrated titanium
dioxide surface can explain the prevailing sorp-
tion of lithium and potassium ions by anatase
and amorphous titanium dioxide at low pH va-
lues (pK around 7) by the presence of a structu-
ral correspondence between the absorbed ion and
the center of sorption — a cavity formed by oxy-
gen atoms. At the same time, taking into ac-
count the proximity of the sizes of potassium
and barium cations, the reason for the similari-
ty of their sorption behavior becomes clear. The
interaction of a cation in the cavity with elect-
rodonor oxygen atoms, which occurs at the sa-
me time, leads to an increase in the energy of
cation-cavity interaction due to the increase of
the covalent component. It is the growth of the
fate of the covalent contribution to the energy of
interaction, on the one hand, and the difference
in the energies of hydration and "solvation" of
the cation cavity, on the other hand, that leads
to a right-hand displacement of the ion-exchan-
ge reaction equilibrium
М–О–H+ + Kat+ → М–О–Kat+ + H+
and determines a noticeable difference in the aci-
dity of the adsorption centers in the absorption of
alkali and alkaline earth metal ions (the first pha-
se of the exchange).
In the second stage, which includes the preli-
minary dissociation of functional hydroxyl groups
that are not part of the cavities, there is no noti-
ceable difference in the acidity of the adsorption
centers, depending on the type of cation.
The third stage of the exchange, most pro-
nounced for amorphous titanium hydroxide, is ob-
viously associated with bridge groups, the amount
of which in amorphous modification must be
much greater, because the formation of titanium
hydroxide occurs through the polymerization step
of polydynamic complexes, which are connected
by the bridge groups.
The analysis of the crystallochemical featu-
res of the structure of the investigated modifica-
tions of titanium hydroxide shows that in the
surface layer of crystallites there are cavities for-
Materials based on titanium and manganese oxides for selective recovery ...
ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2 91
med by different combinations of octahedra [TiO6]
— the main structural unit of the lattice, where
absorbed cations can be located. Considering the
location of oxygen atoms on the facets, we can di-
stinguish three types of cavities. For anatase, the-
se are distorted tetrahedron (oxygen atoms 1–4),
octahedral cavity (5–9), and distorted cube (6–13).
On the surface of the considered face of rutile,
only two types of cavities can be distinguished —
tetrahedral (1–4) and octahedral (5–9). For amor-
phous modifications of hydrated titanium dioxi-
de, it is possible to have all types of cavities fo-
und on the facets of crystalline modifications.
This gives reason to believe that the place of li-
thium cations localization in the first stage can be
tetrahedral cavities, and for potassium cations —
cubic, the absence of which in rutile explains the
difference in the sorption of these cations compa-
red with anatase. The difference in the absorpti-
on of Li+ by these modifications of hydrated tita-
nium dioxide is due, apparently, to the geometric
dimensions of tetrahedral cavities, which are sma-
ller in the anatase because of the difference in
the length of Ti–O bonds. Available on the surfa-
ce of all modifications of titanium dioxide octa-
hedral type cavities when absorbing of alkali and
alkaline earth metal ions are not filled due to the
difference in size [15] (Fig. 1).
Known from the literature the ability of hyd-
rated titanium dioxide to selectively absorb ions
of transition metals, the average ionic radii of
which are in the gap between the sizes of cations
of lithium and potassium, on the one hand, and
the presence on its surface of octahedral cavities
with dimensions, intermediate between tetrahedral
and cubic, on the other hand, allow assuming that
they are the sorption centers of d-metal cations [14].
The proposed structure of the sorption cen-
ters of hydrated titanium dioxide involves inhibi-
tion during simultaneous sorption of ions that are
selectively absorbed. The total amount of sorption
from binary solutions containing lithium and po-
tassium ions is significantly lower than the corres-
ponding values of single-component solutions.
The presence of Na+ in solutions with Li+ practi-
cally does not affect the sorption of the latter, but
the reverse effect is very significant: in the pre-
sence of Li+ or K+ sorption of Na+ is signifi-
cantly reduced. The mechanism of such interac-
tion can be explained by mapping the surface in
the form of charged cavities, the size of which
corresponds to Li+ and K+. In this case, for sorp-
tion from one-component solutions, a certain sur-
face area is capable of absorbing twice the amo-
unt of one ion than when two-component soluti-
on is used. However, the surface of titanium dio-
xide does not contain cavities of the correspon-
ding size of sodium cation, therefore, for sorption
from a multicomponent solution containing ca-
tions of lithium or potassium, sorption of sodium
is practically absent [16].
The main method for obtaining titanium dio-
xide is the hydrolysis of its various salts. At low
pH values, primary products are salts of variable
composition. At higher pH, hydrated forms of ti-
tanium dioxide are formed, the content of water
molecules in which depends on aging and drying
conditions. Freshly deposited titanium dioxide has
a high adsorption capacity both for cations and
anions. The resulting gel is non-porous with par-
ticle size of 30–60 Ao , aggregated into chains or
clusters. The specific surface of the gel is 250–
500 m2/g depending on the conditions of deposi-
tion. During the thermal treatment of gels, it crys-
tallizes to form anhydrous TiO2. Depending on
the heating temperature, polymorphic transfor-
mations of hydrated titanium dioxide into anata-
se, rutile or brookite, accompanied by a change in
the specific surface and porous structure, are pos-
sible. Thus, at temperature below 600 °С, the crys-
Fig. 1. Schematic representation of crystallographic
facets of rutile (a) and anatase (b) with oxygen atoms:
1 – below, 2 – on, and 3 – above the picture plane.
а b
M.O.Chaban, Y.S.Dzyazko, O.V.Bystryk
92 ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2
tallization process proceeds with the formation of
an anatase with practically the same values of po-
re volume and specific surface area. At higher tem-
peratures, the transition of anatase to rutile is obser-
ved, which is accompanied by a sharp decrease in
pore volume and specific surface. Mineral impuri-
ties may also affect the temperature of polymor-
phous transformation. Recently, the sol–gel me-
thod is increasingly used to obtain titanium dioxi-
de, which allows obtaining of nanoscale particles
of titanium dioxide with given structure and pro-
perties. The formation of spherical granules of gel
occurs due to alkaline coagulation of dispersed par-
ticles of hydrosol. Another way of obtaining hyd-
rogels — through the stage of volume neutraliza-
tion of excess acidity of the initial salt solution of
multi-valent metal with ammonia [17].
Sorption properties. According to [18] titani-
um dioxide exhibits anion exchange properties in
acidic and neutral solutions and cation exchange pro-
perties in alkaline solutions. The presence of such
amphoteric properties is explained by the hyd-
rolysis of this oxide with the formation of a surfa-
ce layer of hydroxide and its dissociation in two
directions, with the formation of functional groups
H+ and OH– capable of exchange. Colloidal tita-
nium dioxide is considered to be a sorbent capab-
le of molecular sorption of salts and acids, and
notes that the sorption of neutral salts is negligible
in comparison with sorption of acids [14]. It was
found that from a mixture of two acids — sulfuric
and hydrochloric — the sulfuric acid is adsorbed
predominantly. At a significant equilibrium con-
centration of sodium sulfate (sulfuric acid is for-
med by the interaction of hydrochloric acid con-
taining in ash and sodium sulfate), the dependen-
ce of the sorption of sulfate ions on the pH of the
solution is linear.
Titanium dioxide has cation exchange pro-
perties and in water the reaction of hydrolyzation
occurs as follows:
TiO2 + 2H2O ↔ TiO2(OH)2
2– + 2H+,
where hydrogen ions provide the ability to cation
exchange.
The ion exchange properties of amphoteric
oxides and hydroxides are usually influenced by
two factors. First, the composition and structure
of the sorbent. Available impurities can dramati-
cally change the capacity and selectivity of the ion
exchanger. The structure of the sorbent also has
an effect on the selectivity of the sorption — crys-
talline ionites have a significantly higher selecti-
vity than amorphous. The second factor is the so-
lution parameters, the most important of which is
the concentration of hydrogen ions. Since the most
ion exchangers are weak bases and weak acids,
this dependence is very noticeable.
The patterns of ion exchange on amphoteric
oxides and hydroxides can be explained from the
point of view of two possible mechanisms.
In the first mechanism, functional groups, ca-
pable of exchanging are groups of H+ and OH– on
the surface or in the volume of oxide and hydroxi-
de [18]. In this case, the exchange sorption is usua-
lly strongly dependent on the pH of the solution,
since the dissociation reaction of the acid or base
type with the transition of protons or hydroxyl ions
into the outer part of the double electric layer is de-
termined primarily by the pH of the solution.
The second mechanism of ion exchange re-
lates to materials with impurities capable of sorp-
tion. The impurities may be prepresent in the sor-
bent or formed when material is in contact with
solution. In this case, the amphoteric oxide or
hydroxide functions as a rigid skeleton with fixed
groups capable of exchange. Depending on the na-
ture of the functional groups, these sorbents may
be weak or strong ion exchangers. Often such ion
exchangers have larger capacity than pure oxides
and hydroxides.
Literary data indicate that the following sorp-
tion processes are possible on amphoteric oxides
and hydroxides:
– ion exchange in the primary layer with po-
tential-determining ions (cations in acidic, anions
in alkaline medium);
– ion exchange in the outer layer (anionic in
acid, cationic in alkaline medium);
– simultaneous anion and cation exchange in
the outer layer (near the isoelectric point);
– chemical sorption in acidic medium with the
formation of basic salts and other surface com-
pounds;
Materials based on titanium and manganese oxides for selective recovery ...
ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2 93
– chemical sorption in an alkaline environment
with the formation of aluminates, ferrites, zincates
and other compounds;
– molecular sorption at high concentrations of
electrolyte and close to neutral pH;
– exchange of cations and anions in molecu-
les sorbed by mechanism of molecular sorption
on cations and anions of solution;
– simultaneous sorption of anions with multi-
ply charged cations and cations with multiply char-
ged anions associated with recharging of the surface.
According to the research [19], the adsorp-
tion of double charged metal cations on the surfa-
ce of oxides and hydroxides from solutions of
strong electrolytes does not depend on the electro-
lyte anion (except when the metal forms an amor-
phous complex with an anion), the dependence
of adsorption behavior on ionic strength varies for
different electrolytes. For example, in solutions of
sodium nitrate ionic strength has almost no effect,
in contrast to sodium chloride solutions, in which
the sorption of transition metals decreases with
increasing ionic strength, although NaClO4 solu-
tions are observed to increase of adsorption capa-
city with increasing ionic strength.
Also, the influence of intercalation processes
on the properties of inorganic materials is consi-
dered [20]. Intercalation is reversible topotaxial
chemical reactions with the inclusion of impurity
molecules in the matrix of solids. Such mechanism
allows the synthesis of new compounds with a
complex of unique physico-chemical properties.
"Guest" molecules are embedded in the interlayer
space, which leads to the fact that into the same
matrix molecules quite different in size and geo-
metry can intercalate, that is, the molar-sieve ef-
fect is absent. Relative ease of inclusion in the
interlayer space of hydrated titanium dioxide of va-
rious ions allows to create structures with an ad-
justable composition and the size of interlayer spa-
ce, which have selective ion exchange properties.
Also, in the literature there are investigations
of sorption properties of thermally treated tita-
nium dioxide in comparison with non-treated in
the sorption of several cations. It was found that
the heating of hydroxides to 400 °C does not ef-
fect the amphoteric properties of the material, but
significantly reduces the cation exchange capa-
city of the sorbent by reducing the content of OH-
groups and reducing the surface area. The sorpti-
on capacity of the material correlates with the size
of the hydrated cation, the rate of sorption is de-
termined by the diffusion of cation to the OH-
group, not the ion exchange. However, in some
samples during the calcination, increasing meso-
porosity increases the availability of OH-gro-
ups for exchange, so the dependence of the sorp-
tion rate on the diffusion of hydrated ion is neg-
ligible, as in the case of non-porous gels [21].
Studies [22] demonstrated that ion exchange
characteristics are very dependent on obtaining con-
ditions. And in the study of the distribution coeffi-
cients of some cations, it was found that hydrated
oxides of metals do not have a direct correlation
with change in porosity [23], specific surface area,
and density of the material obtained as a result of
the previous heat treatment. In addition, the distri-
bution coefficients of cobalt ions on crystalline
titanium dioxide increase with increasing tempe-
rature of calcination [24].
Manganese oxides
Porous crystals are interesting with their spe-
cific properties and variety of structures. Alumi-
nosilicates, including zeolites, clay minerals and me-
soporous silicates, can be distinguished as the ma-
in classes, but in recent years attention has been
paid to porous materials from transition metal oxi-
des. Manganese oxides with tunnel and layered
structures can represent a wide range of materials
from ultra-microporous to mesoporous. Most man-
ganese oxide structures consist of octahedras MnO6
separated by angles or facets [25].
Macroporous silicon granules and macropo-
rous gel beads from cellulose were used as car-
riers for selective lithium ion sieves, but their capa-
city was very limited. Other studies have sug-
gested the use of polyvinyl chloride and polysul-
fone for granulation or membrane creation, but it
is difficult to implement on an industrial scale due
to environmental problems with the use of these
materials. Non-woven fabric, which is also used as
a carrier for ion sieve, does not provide sufficient
delay in the particles of the selective material [26].
M.O.Chaban, Y.S.Dzyazko, O.V.Bystryk
94 ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2
It is suggested to create lithium-selective ma-
terial based on polyurethane template method.
Since the obtained foam was porous and inert,
there should not have been a significant reducti-
on in the adsorption capacity/capacity of the in-
troduced material, but this was not confirmed ex-
perimentally. The capacity has dropped signifi-
cantly compared to pure lithium manganate [27].
Since manganese oxides exhibit excellent ca-
tion exchange and adsorption properties, they can
be used as ion sieves, molecular sieves and cata-
lysts, as well as aluminosilicates. The electroche-
mical and magnetic properties of manganese oxi-
des allow their use as cathode materials in lithium
batteries and modern magnetic materials.
Structure of manganese oxides. Today, many
types of tunnel and layered porous manganese
oxide are known. The structural variability of oxi-
des is determined by the reversible conversion be-
tween Mn3+ and Mn4+ and the formation of defects
in crystals.
According to the classification, proposed in
[28] tunnel and layered manganese oxides can be
divided into groups of pyrolusite-ramsdellite with
(1 x n) tunnel structure, hollandite-romanechite with
(2 x n) tunnel structure and todorokite with (3 x n)
tunnel structure. All structures contain chains of
octahedras MnO6, connected by faces, and num-
bers 1, 2, 3 and n show the number of octahedra
along the width of one lattice. Chains, connected
through an angle, form a one-dimensional tunnel
network. When n = 8, the network corresponds to
a layered structure.
Schematically, the structures of some manga-
nese oxides with one-dimensional tunnel and lay-
ered structures are shown in Fig. 2. The structures
of the pyrolusite and ramsdellite have one-dimen-
sional tunnel structures respectively. On the other
hand, oxides such as birnessite and buserite have
layered structures with main ranges of about 0.7
and 1.0 mm, respectively [29].
Metal ions can occupy tunnels of hollandite,
romanechite, todorokite, Rb0.27MnО2, and also the
interlayer space of birnessite. Mangan in oxides
is predominantly quadrivalent, but part of it is tri-
valent to compensate the charge of impurity ions.
Also, in manganese oxides, nonperiodic growth
of two or more tunnel phases is observed. In addi-
tion to one-dimensional (m x n) tunnels, other types
of layered and tunnel structures are also known.
For example, the spinel has a three-dimensional
(1 x 3) network of tunnels with a combination
of 8a tetrahedral units and 16s empty octahedral
units of a cubic dense pack of oxygen lattice. It
is possible to form a series of spinels of the gene-
ral formula LinMn2–xO4 (1 ≤ n ≤ 1.33, 0 ≤ x ≤
0.33, n ≤ 1+x). Typical representatives of this seri-
es are (Li)[MnIIIMnIV]O4 and (Li)[Li0.33MnIV
1.67]O4,
where ( ) and [ ] are 8a tetrahedral and 16d octa-
hedral units, respectively. In the spinel (Li)[MnIII-
MnIV]O4, lithium cation occupies the tetrahed-
ral location of 8a, and the trivalent and quadriva-
lent manganese — 16d octahedral. In (Li)[Li0.33-
MnIV
1.67]O4, lithium is placed at 8a tetrahedral
and free 16d octahedral, and the whole manga-
nese is quadrivalent [30].
Synthesis of ion exchangers based on manga-
nese oxides. Synthesis of ion and molecular sieves
based on manganese oxide can be presented in
two stages: (1) tunnel or layered oxide is prepared
using template ions or molecules to form tunnel
sizes and between spherical cavities; (2) template
ions and molecules are topotactically removed from
the material with the formation of a sieve. Such
manganese oxides can be formed using a variety
of processes that can be conventionally divided
into dry processes (solid phase reactions and inter-
action of salt melts), wet processes (oxidative-re-
ductive deposition, hydrothermal chemical proces-
ses) and mixed processes (sol–gel). Stable phases
Fig. 2. Schematic representation of one-dimensional
tunnel and layered manganese oxides: a – MnO6 octa-
hedron; b – (1x1) tunnel pyrolusite; c – (1x2) tunnel
ramsdellite; d – (1x8) layer lithium-manganese spinel.
a b
dc
Materials based on titanium and manganese oxides for selective recovery ...
ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2 95
with small sized gaps such as spinel, hollandite,
romanechite, and birnessite can be synthesized by
any of these processes. The ion-sieve, electroche-
mical and catalytic properties of manganese oxi-
des often depend on the synthesis conditions.
In solid-phase reactions, the size of obtained
defects in structure depends on the size and amo-
unt of metal ions used as templates. The source
of manganese for such syntheses may be MnCO3,
MnO2, Mn2O3, MnOOH, Mn(CH3COO)2, etc.,
and the source of metal cations is M2CO3, MOH,
MNO3, MCH3COO, and others.
Manganese oxide with spinel structure is pre-
pared using lithium cation. Since manganese oxi-
des play a significant role as cathode materials
in batteries, a large number of studies are devoted
to finding an effective method for their synthesis.
The series of LinMn2–xO4 (1 ≤ n ≤ 1.33, 0 ≤ x ≤
0.33, n ≤ 1+x) oxides can be obtained in the tempe-
rature range of 350–900 °С. The degree of oxidation
of manganese and the composition of the oxide
formed depend on such conditions as the tempera-
ture, the source materials and the atmosphere in
which the synthesis takes place. Spinel (Li)[MnIII-
MnIV]O4 is formed at high temperature (above
700 °С), and spinel (Li)[Li0.33MnIV
1.67]O4 — at
low (below 500 °С) [31].
Ooi and colleagues [32] investigated the
effect of the template alkali metal cation on the
solid-phase reaction process. The authors have
cooled γ-MnO2 saturated with metal ions (Li+,
Na+, K+) at 600 °C for two hours. With lithium
the spinel was obtained, and with cations of sodium
and potassium — hollandite.
Also, some techniques based on the sol–gel
method have been developed to produce spinel [33]
and his colleagues received LiхMn2O4 spinel by
precipitation of Mn(CH3COO)2 solution with li-
thium hydroxide and subsequent precipitate cal-
cination at 300 °C. Scientist [34] received a highly
crystalline spinel Li4Mn5O12 by heating eutectic
mixture of LiOAc and Mn(NO3)2 to 700 °C under
an atmosphere of oxygen. Sol-gel process was de-
veloped for spinel and birnessite [35]. AMnO4 [A
= Li, Na, K, NH4, N(CH3)4] was reduced with for-
mic acid at room temperature until amorphous xe-
rogel was formed. The spinel phase and LiMnO2
were formed during the calcination of the LiMnO4–C4H4O4 gel at 600 and 1000 °C, respectively.
In addition to the above, the methods of syn-
thesis of spinel and birnessite by hydrothermal tre-
atment of γ-MnO2 in solutions of lithium and po-
tassium or sodium hydroxides are also developed.
Sorption properties of manganese oxides. Ooi
divided the adsorption centers of manganese oxi-
des into specific (in volume of the crystal) and
nonspecific (on the crystal surface). Specific cen-
ters in turn are divided into ion exchange and oxi-
dative-reductive [36].
The ion-sieve properties of manganese oxi-
de are investigated by potentiometric titration and
by measurements of the scattering factor. The spi-
nel type ion sieves show a significantly higher sorp-
tion capacity for lithium relative to sodium and po-
tassium, due to the size of lithium ion that can
pass through the tunnel, smaller than the sodium
and potassium ions. Sodium and potassium are
adsorbed on the surface of crystals (non-specific
adsorption), and lithium adsorbs at specific cen-
ters after dehydratation. Although bivalent ions
such as Mg2+, Ni2+, Co2+ are also characterized
by small radii, they do not pass through the tun-
nel, since their dehydratation energy is too high [36].
Hollandite type ion sieves show high values
of capacity for potassium ion at low pH. With
increasing pH, the adsorption capacity increases
with decreasing ion radius, as the steric interac-
tions between metal ions in the tunnel begin to
predominate.
Birnessite ion sieves have different adsorp-
tion properties for small and large ions, for exam-
ple, they are tribasic or dibasic acids relative to
Li+ and monobasic relative to Na+, K+, Cs+
.
Similar characteristics are also given to ion sie-
ves of todorokite type, such as dicarboxylic acids
for lithium, sodium, and potassium ions, and mo-
nobasic for cesium ions. This is since large ions
can be adsorbed only in the center of the tunnel,
while the small ones are located closer to the
walls. The pore radius of the pyrolusite and
ramsdellite is too small for metal ions, so the lat-
ter are adsorbed only on the surface.
The selectivity of the ion sieves of manga-
nese oxide directly depends on their structure. For
M.O.Chaban, Y.S.Dzyazko, O.V.Bystryk
96 ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2
example, for a spinel, the selectivity increases in
the series Na+< K+< Rb+< Cr+<< Li+, for hollan-
dite Li+< Cs+< Na+<< Rb+< K+, for birnessite Li+<
Na+< Cs+,K+< Rb+, and for todorokite Li+< Na+<
K+< Rb+< Cs+. Such dependencies are explained
by the structure of the material: (1x3) the spinel
tunnels fit in size for the lithium ion, (2x3) tun-
nels for potassium and rubidium ions, interlayer
spaces in birnessite correspond to the size of rubi-
dium ion. The dependence of selectivity for todo-
rokite coincides with the growth of the ionic radii
of metals, since all the ions are contained in (3x3)
tunnels.
Volkhin and others found that spinel type
oxide without metallic ions in tunnels can be ob-
tained by extraction of lithium with acid from a
spinel type lithium manganate. Spinel exhibits
adsorption properties to lithium ion [37]. The oxi-
dation-reduction mechanism of the reaction was
proposed:
4(Li)[MnIIIMnIV]O4 + 8H → 3( )[MnIV
2]O4 +
+ 4Li+ + 2Mn2+ + 4H2O .
The driving force for delitiation is the dispro-
portionation reaction of MnIII to MnIV and MnII in
acidic medium. The oxidative-reducive release of
one lithium cation is provided by the dispropor-
tionation of one MnIII atom by the reaction
MnIII → 1/2MnIV + 1/2MnII,
in the non-lithium spinel the whole manganese is
quadrivalent.
When lithium is adsorbed, there is an inver-
se reaction of the transition of a part of tetravalent
manganese to trivalent with the release of oxygen.
( )[MnIV
2]O4 + LiOH → (Li)[MnIIIMnIV]O4 +
+ 0.5H2O + 0,25O2 .
On the other hand, there is also ion exchange
mechanism for the adsorption/release of lithium
ion. Studies have shown that the choice of an oxi-
dative-reductive or ion-exchange mechanism de-
pends on the degree of oxidation of manganese
and the distribution of metal ions in the spinel. The
reaction of ion exchange is as follows:
(Li)[Li0.33MnIV
1.67]O4 + 1.33H+ ↔
↔ (H)[H0.33MnIV
1.67]O4 + 1.33Li+ .
In this spinel, the whole manganese is quad-
rivalent (λ-MnO2), so the dispersion reaction do-
es not occur in the acidic medium. In the spinel
structure, one MnIII ion corresponds to one oxi-
dative-reductive center, and one Mn defect in the
16d octahedral structure corresponds to four ion-
exchange centers. In most real spinels there are
both oxidative-reductive and ion-exchange cen-
ters, number of each depends on the conditions
of the spinel [38].
Another variant of this type of manganese
oxides can be obtained by introducing bivalent and
trivalent metal cations into the lithium manganese
spinel. The oxidative-reducive spinel contains
metal ions that can be oxidized to higher valences
when lithium cations leave spinel cavities.
The spinel type manganese oxides exhibit
selectivity to lithium against sodium and potas-
sium, as lithium cation due to a small radius can
penetrate the spinel structure tunnel without po-
tassium and sodium cations. The latter are non-
selectively adsorbed on the surface of the crystal,
while Li+ adsorbed on specific centers after de-
hydratation.
CONCLUSIONS. It is possible to satisfy the
demand due to the effective removal of lithium
from cheap primary or secondary resources, in
particular by obtaining it from brines or sea water,
where the most promising is the use of ion-ex-
change selective materials.
Hydrated titanium dioxide contains in its
structure cavities of various shapes and sizes,
which may allow sorption of certain ions, without
dissociation of functional groups. And with the
help of directed thermal synthesis it is possible
to create a certain size of cavities in the structure
of hydrated titanium dioxide.
Lithium magnesium spinels are the most sui-
table for sorption of lithium ions, due to high
selectivity for lithium and a good sorption capa-
city, but these compounds are characterized by
unsatisfactory physical properties due to the fra-
gility of the material. The combination of the
material formed on the basis of hydrated tita-
nium dioxide with known lithium manganese
Materials based on titanium and manganese oxides for selective recovery ...
ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2 97
spinels allows to obtain a strong ion-exchange ma-
terial for the selective extraction of lithium ions.
МАТЕРІАЛИ НА ОСНОВІ ОКСИДІВ ТИТАНУ І
МАНГАНУ ДЛЯ СЕЛЕКТИВНОГО ВИЛУЧЕННЯ
ЛІТІЮ З ВОДНИХ ДЖЕРЕЛ
М.О. Чабан*, Ю.С. Дзязько, О.В. Бистрик
Інститут загальної та неорганічної хімії
ім. В.І.Вернадського НAH України, просп. Ака-
деміка Палладіна, 32/34, Київ, 03142, Україна
* e-mail: mary.chaban@gmail.com
Через постійно зростаюче виробництво еле-
ктронних портативних пристроїв, в тому числі га-
джетів, для одержання літій-іонних акумуляторів
необхідно шукати способи вилучення літію. Лі-
тій є електрохімічно активним, має найвище зна-
чення окисно-відновного потенціалу і найвищу
питому теплоємність серед твердих матеріалів, що
робить його ключовим елементом у сучасній ре-
волюції електричних транспортних засобів. Зем-
на кора містить близько 0.007 % літію, не у чисто-
му вигляді, а його незначні концентрації виявля-
ються практично у всіх вулканічних породах, а
також у водах мінеральних джерел, морській во-
ді та океанах. Існує більше 20 мінералів, що міс-
тять літій, але лише деякі з них мають вміст, дос-
татній, щоб викликати комерційний інтерес. Перс-
пективним напрямком є переробка розсолів, що
утворюються після опріснення морської води і
шахтних вод. Цей напрямок вважається екологі-
чно чистим і рентабельним. Оскільки концентра-
ція літію в таких ресурсах є низькою, сорбційні ме-
тоди видаються більш доречними, порівняно з ін-
шими. У даній статті описані матеріали, що широ-
ко вивчаються з метою отримання літій-селектив-
них адсорбентів. Більшість амфотерних оксидів і
гідроксидів є амфотерними йонообмінниками, що
здатні як до катіонного, так і до аніонного обміну.
Ці матеріали представляють науковий інтерес у
зв’язку з вивченням поведінки радіоактивних ізо-
топів, дезактивації стічних вод та концентруван-
ня мікрокількостей елементів. Синтез таких іоно-
обмінників, як амфотерні оксиди і гідроксиди, є
досить простим, і їхня вартість на одиницю ємно-
сті в більшості випадків набагато нижче, ніж ор-
ганічних смол. Комбінація матеріалів на основі
гідратованого діоксиду титану з відомими літіє-
вими марганцевими шпінелями дозволяє отри-
мати іонообмінний матеріал для селективного ви-
лучення іонів літію.
К л ю ч о в і с л о в а: діоксид титану, оксид
мангану, літій, іонний обмін.
МАТЕРИАЛЫ НА ОСНОВЕ ОКСИДОВ ТИТАНА И
МАРГАНЦА ДЛЯ СЕЛЕКТИВНОГО ИЗВЛЕЧЕНИЯ
ЛИТИЯ ИЗ ВОДНЫХ ИСТОЧНИКОВ
М.А.Чабан*, Ю.С.Дзязько, О.В.Быстрик
Институт общей и неорганической химии
им. В.И.Вернадского НАН Украины, просп. Ака-
демика Палладина, 32/34, Киев, 03142, Украина
* e-mail: mary.chaban@gmail.com
Из-за постоянно растущего производства эле-
ктронных портативных устройств, в том числе га-
джетов, для получения литий-ионных аккумуля-
торов необходимо искать способы извлечения ли-
тия. Земная кора содержит около 0.007 % лития, не
в чистом виде, а его незначительные концентра-
ции оказываются практически во всех вулкани-
ческих породах, а также в водах минеральных ис-
точников, морской воде и океанах. Существует бо-
лее 20 минералов, содержащих литий, но лишь
немногие из них имеют содержание, достаточное,
чтобы вызвать коммерческий интерес. Перспек-
тивным направлением является переработка рас-
солов, образующихся после опреснения морской
воды и шахтных вод. Это направление считается
экологически чистым и рентабельным. Поскольку
концентрация лития в таких ресурсах низкая, сорб-
ционные методы кажутся более уместными, по
сравнению с другими. В данной статье описаны
материалы, которые широко изучаются с целью
получения литий-селективных адсорбентов. Боль-
шинство амфотерных оксидов и гидроксидов яв-
ляются амфотерными ионообменниками, способ-
ными как к катионному, так и к анионному обме-
ну. Такие материалы представляют научный ин-
терес в связи с изучением поведения радиоакти-
вных изотопов, дезактивации сточных вод и кон-
центрирования микроколичеств элементов.
К л ю ч е в ы е с л о в а: диоксид титана, оксид
марганца, литий, ионный обмен.
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Received 05.04.2019
M.O.Chaban, Y.S.Dzyazko, O.V.Bystryk
100 ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 2
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| institution | Ukrainian Chemistry Journal |
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| language | English |
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| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
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| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-312026-07-22T08:23:40Z MATERIALS BASED ON TITANIUM AND MANGANESE OXIDES FOR SELECTIVE RECOVERY OF LITHIUM FROM WATER SOURCES МАТЕРИАЛЫ НА ОСНОВЕ ОКСИДОВ ТИТАНА И МАРГАНЦА ДЛЯ СЕЛЕКТИВНОГО ИЗВЛЕЧЕНИЯ ЛИТИЯ ИЗ ВОДНЫХ ИСТОЧНИКОВ МАТЕРІАЛИ НА ОСНОВІ ОКСИДІВ ТИТАНУ І МАНГАНУ ДЛЯ СЕЛЕКТИВНОГО ВИЛУЧЕННЯ ЛІТІЮ З ВОДНИХ ДЖЕРЕЛ Dzyazko, Yuliya Chaban, Mariya Bystryk, Olga titanium dioxide, manganese oxide, lithium, ion exchange. диоксид титана, оксид марганца, литий, ионный обмен. діоксид титану, оксид мангану, літій, йонний обмін. Due to the ever-increasing production of electronic portable devices, including gadgets, lithium recovery is used to produce lithium-ion batteries. Lithium is electrochemically active, has the highest value of oxidation-reducing potential and the highest specific heat capacity among solid materials, making it a key element in the modern revolution of electric vehicles. The crust contains about 0.007% lithium, which is not in its pure form, but its insignificant concentrations are found in virtually all volcanic rocks and in the waters of mineral springs, sea water, and oceans. There are more than 20 minerals that contain lithium, but only few of them have content that is sufficient for commercial interest. A promising area is the processing of brines that are formed after desalination of seawater and mine waters. It is environmentally friendly and cost-effective. Since the concentration of lithium in such resources is low, sorption methods are advantageous compared to other. In this article materials that are widely studied in order to produce lithium-selective adsorbents are described. Most amphoteric oxides and hydroxides are amphoteric ion exchanges having both cation exchange and anion exchange properties. Such materials are of scientific interest in connection with the study of fission fragments behavior, release of radioactive isotopes, decontamination of sewage and concentration of microquantities of elements. The synthesis of such ion exchangers as amphoteric oxides and hydroxides is fairly simple and their cost per unit of capacity in most cases is much lower than the cost of organic resins. The combination of the material formed on the basis of hydrated titanium dioxide with known lithium manganese spinels allows to obtain a strong ion-exchange material for the selective extraction of lithium ions. Благодаря постоянно растущему производству электронных портативных устройств, в том числе гаджетов, для получения литий-ионных аккумуляторов необходимо искать способы извлечения лития. Земная кора содержит около 0,007% лития, не в чистом виде, а его незначительные концентрации оказываются практически во всех вулканических породах, а также в водах минеральных источников, морской воде и океанах. Существует более 20 минералов, содержащих литий, но лишь немногие из них имеют содержание, достаточное для коммерческого интереса. Перспективным направлением является переработка рассолов, образующихся после опреснения морской воды и шахтных вод. Такое направление считается экологически чистым и рентабельным. Поскольку концентрация лития в таких ресурсах низкая, сорбционные методы кажутся более уместными, по сравнению с другими. В данной статье описаны материалы, которые широко изучаются с целью получения литий-селективных адсорбентов. Большинство амфотерных оксидов и гидроксидов являются амфотерными ионообменниками, способными как к катионному обмену, так и к анионному обмену. Такие материалы представляют научный интерес в связи с изучением поведения радиоактивных изотопов, дезактивации сточных вод и концентрирования микроколичеств элементов. Завдяки постійно зростаючому виробництву електронних портативних пристроїв, в тому числі гаджетів, для одержання літій-іонних акумуляторів необхідно шукати способи вилучення літію. Літій є електрохімічно активним, має найвище значення окисно-відновного потенціалу і найвищу питому теплоємність серед твердих матеріалів, що робить його ключовим елементом у сучасній революції електричних транспортних засобів. Земна кора містить близько 0,007% літію, не у чистому вигляді, а його незначні концентрації виявляються практично у всіх вулканічних породах, а також у водах мінеральних джерел, морській воді та океанах. Існує більше 20 мінералів, що містять літій, але лише деякі з них мають вміст, достатній для комерційного інтересу. Перспективним напрямком є переробка розсолів, що утворюються після опріснення морської води і шахтних вод. Такий напрямок вважається екологічно чистим і рентабельним. Оскільки концентрація літію в таких ресурсах є низькою, сорбційні методи видаються більш доречними, порівняно з іншими. У даній статті описані матеріали, що широко вивчаються з метою отримання літій-селективних адсорбентів. Більшість амфотерних оксидів і гідроксидів є амфотерними йонообмінниками, що здатні як до катіонного обміну, так і до аніонного обміну. Такі матеріали представляють науковий інтерес у зв'язку з вивченням поведінки радіоактивних ізотопів, дезактивації стічних вод та концентрування мікрокількостей елементів. Синтез таких іонообмінників, як амфотерні оксиди і гідроксиди, є досить простим, і їхня вартість на одиницю ємності в більшості випадків набагато нижче, ніж вартість органічних смол. Комбінація матеріалів на основі гідратованого діоксиду титану з відомими літієвими марганцевими шпінелями дозволяє отримати іонообмінний матеріал для селективного вилучення іонів літію. V.I.Vernadsky Institute of General and Inorganic Chemistry 2019-02-15 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/31 10.33609/0041-6045.85.2.2019.88-100 Ukrainian Chemistry Journal; Vol. 85 No. 2 (2019): Ukrainian Chemistry Journal; 88-100 Украинский химический журнал; ##issue.vol## 85 ##issue.no## 2 (2019): Украинский химический журнал; 88-100 Український хімічний журнал; Том 85 № 2 (2019): Український хімічний журнал; 88-100 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/31/13 Copyright (c) 2019 Yuliya Dzyazko, Mariya Chaban, Olga Bystryk https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | діоксид титану оксид мангану літій йонний обмін. Dzyazko, Yuliya Chaban, Mariya Bystryk, Olga МАТЕРІАЛИ НА ОСНОВІ ОКСИДІВ ТИТАНУ І МАНГАНУ ДЛЯ СЕЛЕКТИВНОГО ВИЛУЧЕННЯ ЛІТІЮ З ВОДНИХ ДЖЕРЕЛ |
| title | МАТЕРІАЛИ НА ОСНОВІ ОКСИДІВ ТИТАНУ І МАНГАНУ ДЛЯ СЕЛЕКТИВНОГО ВИЛУЧЕННЯ ЛІТІЮ З ВОДНИХ ДЖЕРЕЛ |
| title_alt | MATERIALS BASED ON TITANIUM AND MANGANESE OXIDES FOR SELECTIVE RECOVERY OF LITHIUM FROM WATER SOURCES МАТЕРИАЛЫ НА ОСНОВЕ ОКСИДОВ ТИТАНА И МАРГАНЦА ДЛЯ СЕЛЕКТИВНОГО ИЗВЛЕЧЕНИЯ ЛИТИЯ ИЗ ВОДНЫХ ИСТОЧНИКОВ |
| title_full | МАТЕРІАЛИ НА ОСНОВІ ОКСИДІВ ТИТАНУ І МАНГАНУ ДЛЯ СЕЛЕКТИВНОГО ВИЛУЧЕННЯ ЛІТІЮ З ВОДНИХ ДЖЕРЕЛ |
| title_fullStr | МАТЕРІАЛИ НА ОСНОВІ ОКСИДІВ ТИТАНУ І МАНГАНУ ДЛЯ СЕЛЕКТИВНОГО ВИЛУЧЕННЯ ЛІТІЮ З ВОДНИХ ДЖЕРЕЛ |
| title_full_unstemmed | МАТЕРІАЛИ НА ОСНОВІ ОКСИДІВ ТИТАНУ І МАНГАНУ ДЛЯ СЕЛЕКТИВНОГО ВИЛУЧЕННЯ ЛІТІЮ З ВОДНИХ ДЖЕРЕЛ |
| title_short | МАТЕРІАЛИ НА ОСНОВІ ОКСИДІВ ТИТАНУ І МАНГАНУ ДЛЯ СЕЛЕКТИВНОГО ВИЛУЧЕННЯ ЛІТІЮ З ВОДНИХ ДЖЕРЕЛ |
| title_sort | матеріали на основі оксидів титану і мангану для селективного вилучення літію з водних джерел |
| topic | діоксид титану оксид мангану літій йонний обмін. |
| topic_facet | titanium dioxide manganese oxide lithium ion exchange. диоксид титана оксид марганца литий ионный обмен. діоксид титану оксид мангану літій йонний обмін. |
| url | https://ucj.org.ua/index.php/journal/article/view/31 |
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