New effective sorbents for purification of aqueous media from technogenic contaminants
Created are the sorbents based on silica gel non-covalently modified with partially hydrogenated heterocyclic compounds (PHHC), containing nitrogen as donor atoms for purification of aqueous media from technogenic contaminants. The investigations show that the modified silica gel is characterized by...
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| Zitieren: | New effective sorbents for purification of aqueous media from technogenic contaminants / T.A. Blank, K.N. Belikov, K.Yu. Bryleva, I. B. -Kh.Shcherbakov, V.A. Chebanov, E.A. Muravyova, V.E. Saraev, I.M. Zviagin, S.A. Komykhov, K.S. Ostras, V.N. Chernenko // Functional Materials. — 2017. — Т. 24, № 4. — С. 706-714. — Бібліогр.: 23 назв. — англ. |
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Blank, T.A. Belikov, K.N. Bryleva, K.Yu. Shcherbakov, I. B.-Kh. Chebanov, V.A. Muravyova, E.A. Saraev, V.E. Zviagin, I.M. Komykhov, S.A. Ostras, K.S. Chernenko, V.N. 2018-06-16T17:19:20Z 2018-06-16T17:19:20Z 2017 New effective sorbents for purification of aqueous media from technogenic contaminants / T.A. Blank, K.N. Belikov, K.Yu. Bryleva, I. B. -Kh.Shcherbakov, V.A. Chebanov, E.A. Muravyova, V.E. Saraev, I.M. Zviagin, S.A. Komykhov, K.S. Ostras, V.N. Chernenko // Functional Materials. — 2017. — Т. 24, № 4. — С. 706-714. — Бібліогр.: 23 назв. — англ. 1027-5495 DOI: https://doi.org/10.15407/fm24.04.706 https://nasplib.isofts.kiev.ua/handle/123456789/136882 Created are the sorbents based on silica gel non-covalently modified with partially hydrogenated heterocyclic compounds (PHHC), containing nitrogen as donor atoms for purification of aqueous media from technogenic contaminants. The investigations show that the modified silica gel is characterized by a sorption capacity relatively higher than that of unmodified one. The sorption degree of metal ions is studied depending on their concentrations, total mineralization and pH value of the solutions. Conditions for selective sorption of microquantities of Eu³⁺ which has been used as chemically identical to ²⁴¹Am are described. Moreover it was shown that PHHC modified silica gel was potential to use as the sorbent to concentrate the Eu³⁺ and Sr²⁺ metal ions with initial concentrations near 1 mg∙L⁻¹ for the quantitative analysis. Also the possible mechanism of metal ion sorption on the developed sorbents was proposed. Remove selected en НТК «Інститут монокристалів» НАН України Functional Materials Green chemistry New effective sorbents for purification of aqueous media from technogenic contaminants Article published earlier |
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New effective sorbents for purification of aqueous media from technogenic contaminants |
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New effective sorbents for purification of aqueous media from technogenic contaminants Blank, T.A. Belikov, K.N. Bryleva, K.Yu. Shcherbakov, I. B.-Kh. Chebanov, V.A. Muravyova, E.A. Saraev, V.E. Zviagin, I.M. Komykhov, S.A. Ostras, K.S. Chernenko, V.N. Green chemistry |
| title_short |
New effective sorbents for purification of aqueous media from technogenic contaminants |
| title_full |
New effective sorbents for purification of aqueous media from technogenic contaminants |
| title_fullStr |
New effective sorbents for purification of aqueous media from technogenic contaminants |
| title_full_unstemmed |
New effective sorbents for purification of aqueous media from technogenic contaminants |
| title_sort |
new effective sorbents for purification of aqueous media from technogenic contaminants |
| author |
Blank, T.A. Belikov, K.N. Bryleva, K.Yu. Shcherbakov, I. B.-Kh. Chebanov, V.A. Muravyova, E.A. Saraev, V.E. Zviagin, I.M. Komykhov, S.A. Ostras, K.S. Chernenko, V.N. |
| author_facet |
Blank, T.A. Belikov, K.N. Bryleva, K.Yu. Shcherbakov, I. B.-Kh. Chebanov, V.A. Muravyova, E.A. Saraev, V.E. Zviagin, I.M. Komykhov, S.A. Ostras, K.S. Chernenko, V.N. |
| topic |
Green chemistry |
| topic_facet |
Green chemistry |
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2017 |
| language |
English |
| container_title |
Functional Materials |
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НТК «Інститут монокристалів» НАН України |
| format |
Article |
| description |
Created are the sorbents based on silica gel non-covalently modified with partially hydrogenated heterocyclic compounds (PHHC), containing nitrogen as donor atoms for purification of aqueous media from technogenic contaminants. The investigations show that the modified silica gel is characterized by a sorption capacity relatively higher than that of unmodified one. The sorption degree of metal ions is studied depending on their concentrations, total mineralization and pH value of the solutions. Conditions for selective sorption of microquantities of Eu³⁺ which has been used as chemically identical to ²⁴¹Am are described. Moreover it was shown that PHHC modified silica gel was potential to use as the sorbent to concentrate the Eu³⁺ and Sr²⁺ metal ions with initial concentrations near 1 mg∙L⁻¹ for the quantitative analysis. Also the possible mechanism of metal ion sorption on the developed sorbents was proposed.
Remove selected
|
| issn |
1027-5495 |
| url |
https://nasplib.isofts.kiev.ua/handle/123456789/136882 |
| citation_txt |
New effective sorbents for purification of aqueous media from technogenic contaminants / T.A. Blank, K.N. Belikov, K.Yu. Bryleva, I. B. -Kh.Shcherbakov, V.A. Chebanov, E.A. Muravyova, V.E. Saraev, I.M. Zviagin, S.A. Komykhov, K.S. Ostras, V.N. Chernenko // Functional Materials. — 2017. — Т. 24, № 4. — С. 706-714. — Бібліогр.: 23 назв. — англ. |
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2025-11-26T15:25:10Z |
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| fulltext |
706 Functional materials, 24, 4, 2017
ISSN 1027-5495. Functional Materials, 24, No.4 (2017), p. 706-714
doi:https://doi.org/10.15407/fm24.04.706 © 2017 — STC “Institute for Single Crystals”
New effective sorbents for purification of aqueous
media from technogenic contaminants
S.V.Khimchenko1, T.A.Blank1, K.N.Belikov1,2, K.Yu.Bryleva1,
I. B.-Kh.Shcherbakov1, V.A.Chebanov1,2, E.A.Muravyova1,
V.E.Saraev 1, I.M.Zviagin1, S.A.Komykhov 1,2,
K.S.Ostras1, V.N. Chernenko 1,2
1 SSI “Institute for Single Crystals”, National Academy of Sciences
of Ukraine, 60 Nauky ave., Kharkiv 61178, Ukraine
2 V.N.Karazin Kharkiv National University, 4 Svobody sq.,
Kharkiv 61077, Ukraine
Received July 7, 2017
Created are the sorbents based on silica gel non-covalently modified with partially hydroge-
nated heterocyclic compounds (PHHC), containing nitrogen as donor atoms for purification of
aqueous media from technogenic contaminants. The investigations show that the modified silica
gel is characterized by a sorption capacity relatively higher than that of unmodified one. The
sorption degree of metal ions is studied depending on their concentrations, total mineralization
and pH value of the solutions. Conditions for selective sorption of microquantities of Eu3+ which
has been used as chemically identical to 241Am are described. Moreover it was shown that PHHC-
modified silica gel was potential to use as the sorbent to concentrate the Eu3+ and Sr2+ metal ions
with initial concentrations near 1 mg∙L–1 for the quantitative analysis. Also the possible mecha-
nism of metal ion sorption on the developed sorbents was proposed.
Keywords: sorbent, modified silica gel, sorption degree, partially hydrogenated heterocyclic
compounds, metal ions.
Разработаны сорбенты на основе силикагеля, нековалентно модифицированного частично
гидрированными гетероциклическими соединениями (PHHC), содержащими азот в качестве
донорных атомов, для очистки водных сред от техногенных загрязнений. Показано, что
модифицированный силикагель по сравнению с немодифицированным характеризуется более
высокой сорбционной емкостью. Получены экспериментальные зависимости степени сорбции
ионов металлов на разработанных сорбентах от величины рН и общей минерализации растворов.
установлены концентрационные зависимости степени сорбции металло-ионов из водных
растворов. Описаны условия селективной сорбции микросодержаний Eu3+, который использовался
в качестве химического аналога 241Am. Показано, что силикагель, модифицированный PHHC,
также пригоден для концентрировании металло-ионов Eu3 + и Sr2 + с начальными концентрациями
около 1 мг∙л–1 при проведении количественного анализа. Описан возможный механизм сорбции
металло-ионов на разработанных сорбентах.
Functional materials, 24, 34 2017 707
S.V.Khimchenko et al. / New effective sorbents for purification ...
1. Introduction
intensity of mining-metallurgical and nucle-
ar industries has led to significant dispersion
and deposition of heavy metals and technogenic
radionuclides of different origin in the environ-
ment [1]. One of the impacts is visible, in form
of water pollution [2]. There is an obvious need
for industrial technologies for deactivation
and cleaning of great amounts of surface and
ground water, swamp and river ecosystems,
soils [1].The conventional methods of treat-
ment of heavy metal and radionuclide contami-
nation include chemical precipitation, chemical
oxidation or reduction, ion exchange, filtration,
electrochemical treatment, membrane separa-
tion, reverse osmosis, electro dialysis, evapora-
tion recovery etc. [3] These methods are costly,
energy intensive and often associated with
generation of toxic byproducts [2, 4]. Moreover
these processes may occur to be ineffective or
extremely expensive, especially when the met-
als in solution are in the concentration below
1 mg·L–1 [3]. Therefore environmental stud-
ies are confronted with a challenging task to
develop appropriate low cost technologies for
treatment of liquid wastes [3]. Adsorption has
emerged out to be better alternative treatment
methods [1– 3].
Adsorption is basically a mass transfer pro-
cess by which a substance is transferred from
the liquid phase to the surface of a solid, and
becomes bound by physical and/or chemical in-
teractions. It is a partition process in which few
components of the liquid phase are relocated to
the surface of the solid adsorbents. In general,
the main steps involved in adsorption of pol-
lutants on solid adsorbent are: transport of the
pollutant from bulk solution to external surface
of the adsorbent; internal mass transfer by pore
diffusion from outer surface of adsorbent to the
inner surface of porous structure; adsorption
of adsorbate on the active sites of the pores of
adsorbent. The overall rate of adsorption is de-
cided by either film formation or intra particle
diffusion or both as the last step of adsorption
are rapid as compared to the remaining two
steps [2]. Selective sorption of radionuclides al-
lows to concentrate long-lived radionuclides in
a small volume of sorbent and simplify treat-
ment technology for liquid radioactive waste. Cur-
rently adsorption seems to be the easiest, safest
and most cost-effective method for treatment of
waste effluents containing heavy metals. The key
benefit of adsorption method for heavy metal
and radionuclide contamination removal is less
initial as well as operation cost, unproblematic
design and less requirement of control systems
[2]. Unlike conventional methods adsorption is
suitable even when heavy metals and radionu-
clides are present at concentrations as low as
1 mg∙L–1 [2, 3]. Therefore adsorption methods
are mainly used for deep purification and post-
treatment of sewage. According to the literature
data, the efficiency of adsorption treatment of
waste water reaches 80 – 95% [5].
To be commercially viable, an adsorbent
should have high selectivity to facilitate quick
separations, favorable transport and kinetic
characteristics, thermal and chemical stability,
mechanical strength, resistance to fouling, low
solubility in the liquid in contact [2]. Moreover,
environmentally safeness of waste sorbents
disposal is required. Silica gels are chemically
inert, non-toxic materials composed of amor-
phous silicon dioxide. They are characterized
by a highly porous texture and therefore they
can be utilized for synthesis of adsorbents with
Нові ефективні сорбенти для очищення водних середовищ від техногенних
забруднень. С.В.Химченко, Т.А.Бланк, К.М.Бєліков, К.Ю.Брильова, І.Б.-Х.Щербаков,
В.А.Чебанов, О.О. Муравйова, В.Є.Сараєв, Є.М.Звягін , С.О.Комихов, К.С.Острась,
В.М.Черненко
Розроблені сорбенти на основі силікагелю, який був нековалентно модифікований
частково гідрованими гетероциклічними сполуками (PHHC), що містять азот в якості
донорних атомів для очищення водних середовищ від техногенних забруднень.
Показано, що модифікований силікагель має більш високу сорбційну ємність ніж
немодифікований. Отримано експериментальні залежності ступеня сорбції іонів
металів на розроблених сорбентах від величини рН та загальної мінералізації розчинів.
Встановлено концентраційні залежності ступеня сорбції метало-іонів із водних розчинів.
Описано умови селективної сорбції мікрокількісного вмісту Eu3 +, який був використаний
в якості хімічного аналога 241Am. Показано, що силікагель, модифікований PHHC, також
придатний для концентрування метало-іонів Eu3+ і Sr2+ із початковими концентраціями
близько 1 мг∙л–1 під час проведення кількісного аналізу. Був запропонований можливий
механізм сорбції метало-іонів на розроблених сорбентах.
708 Functional materials, 24, 4, 2017
S.V.Khimchenko et al. / New effective sorbents for purification ...
preset structural characteristics and various
chemical surfaces. In addition, the structure of
silica gel is corpuscular, i.e. it consists of inter-
connected particles forming a three-dimension-
al skeleton. The particle size affects the value
of the specific surface area, while the compact-
ness of binding influences the absorption vol-
ume of the pores [6]. Adsorption properties of
silica gel have been attributed to the surface
hydroxyl groups of silica gel. Some hydroxyl
groups are free standing and called free silanol
groups. Some are hydrogen bonded to neigh-
bouring silanol groups [7]. These groups enable
the attachment of organic molecules, which can
coordinate metal ions in a solution [6]. Recently,
surface functionalization of ordered silica gel
has attracted intensive interest in view of its
use as a solid support, due to its large spe-
cific surface area and fast adsorption kinetics
[6, 8]. Physically or chemically modified silica
gels with organic or inorganic compounds have
been used widely as solid phases to preconcen-
trate metal ions from different kind of natural
samples such as sea water, river water, bio-
logical samples, etc. [9]. The correct choice of a
desired functional group for immobilization on
the silica surface can yield materials that are
highly selective for a specific contaminant [6].
Partially hydrogenated heterocyclic compounds
containing functional groups capable of form-
ing covalent chemical bonds by a donor-accep-
tor mechanism with radionuclides and heavy
metal ions [10–12] can act as suitable organic
agents for silica gel modification. A number of
techniques can be used to fix an analytical re-
agent on a matrix. One of them is a synthetic
method involving the so-called covalent graft-
ing of a modifying reagent. Another method is
impregnation of a matrix with a solution of a
modifier [13]. Non-covalently modified sorbents
possess a number of advantages, in particular,
ease of preparation and sufficient stability. At
the same time the sorption properties of such
materials are defined by the complexing prop-
erties of immobilized organic reagents [14–15].
The goal of the present paper is to synthe-
size sorbents based on silica gel non-covalently
modified with partially hydrogenated hetero-
cyclic compounds (PHHC), containing nitrogen
as donor atoms, with selective sorption toward
heavy metals and radionuclides .
2. Materials and methods
2.1. General
The residual concentration of the target
metal ion in the solution after sorption was
determined by atomic emission spectroscopy
with inductively coupled plasma (AES-ICP) on
a spectrometer of TRACE SCAN Advantage
(Thermo Jarrell Ash, USA). Absorption spectra
were recorded using a SF-2000-02 spectropho-
tometer (OKB “Spectrum”, St. Petersburg, Rus-
sia). The solution pH was measured using a рН
OHAUS STARTER 3100 pH meter (OHAUS,
USA). The solutions were stirred with a magnetic
stirrer MS300 (ULAB, PRC). The residual con-
centration of the PHHC on the adsorbent surface
after sorption was determined using a EuroEA-
3000 elemental analyzer (EuroVector, Italy).
All chemicals and solvents used for the syn-
thesis, photometric measurements and adsor-
bent properties investigations were of analyti-
cal reagent grade, and used without further pu-
rification unless otherwise specified.
Original Silica Gel brand C-60 for column
chromatography with an average pore diame-
ter of 60 Е, the mean pore volume of 0.75 ml / g
and with specific surface area of 500 m2/g came
from Ross (Belgium).
Merrifield Peptide Resin (particle size 100–
200 mesh) came from Sigma-Aldrich.
The metal ions studied were Eu3+, Cu2+, Sr2+.
The former was used as chemically identical to
241Am. The stock standard solutions with the
concentration 1 mg∙L-1 were prepared with ul-
trapure water obtained on a “P.NIX POWER
SYSTEM” (“HUMAN CORPORATION”, South
Scheme 1. Structures of A – E.
Functional materials, 24, 34 2017 709
S.V.Khimchenko et al. / New effective sorbents for purification ...
Korea) from standard 1000 mg∙L–1 solutions
(Sigma-Aldrich).
Whatman® quantitative filter paper, ash-
less, Grade 589/2 white ribbon came from Sig-
ma-Aldrich.
2.2. Synthesis of the PHHC
Compounds A -C (Scheme 1) were pre-
pared according to a published procedure
[16, 17] by three-component reaction of corre-
sponding aminoazole (3-amino-1,2,4-triazole
for A, 5-amino-3-methyl-1-phenylpyrazole
for B, 5-amino-3-methylisoxazole for C) with
3-hydroxybenzaldehyde and methylene-active
compound (o-acetoacetanisidide, dimedone) by
heating in dimethylformamide with yields of
80% for A, 68 % for B and 84% for C.
Compound D (Scheme 1, D) was prepared ac-
cording to a published procedure [18] by reaction
of salicylaldehyde and aqueous ammonia and
washing of the obtained precipitate with ethanol;
the yield of the crude product was 92%.
Compound E was prepared according to de-
scribed procedure [19] from 3-amino-1,2,4-tri-
azole and 2’-hydroxychalcone by heating of the
initial substances in dimethylformamide for 20
minutes with 85 % yield of the crude product.
2.3. UV–vis measurements
Photometric measurements were performed
in 1 cm quartz cuvettes. The estimations of λmax
(in nm) were performed with a program includ-
ed in the spectrophotometer software package,
running in a mode “Register the absorption
spectrum”. The concentration of the PHHC in
the solutions for photometry was higher than
the metal concentration by 2, 6 or 9 times. The
PHHC dissolved in a suitable solvent with the
addition of 1 M nitric acid (for pH equal to
blank and working solutions), was used as a
blank solution.
2.4. Preparation of sorbents
Synthesis impregnated by the PHHC sorbents
based on Silica Gel
Original Silica Gel was pre-washed with 10%
hydrochloric acid and dried under vacuum for 6
hours at 120o C. PHHC (0.2 g) was dissolved
in 50 ml of the solvent (chloroform, ethanol or
DMF) at room temperature. In a beaker with
1 g of silica gel 25 ml of the PHHC solution was
added. The mixture was stirred for 30 minutes
on a magnetic stirrer. Then the precipitate was
filtered on a paper filter. Afterwards the sor-
bent was dried at 80°С to constant weight.
Table 1. Spectral characteristics of the complexes with some organic compounds which are suitable for
creation of hybrid sorbents
Organic com-
pounds
Solvent of
the complex
Target metal
ion
Ratio of ligand:
metal concentra-
tions
рН λmax, nm Optical den-
sity
A DMF
Sr 6:1 7 320 0.32
Cu 6:1 7 388 0.84
Eu 6:1 7 391 0.71
D Ethanol Eu 6:1 6 451 0.80
Cu 6:1 6 400 1.40
B Ethanol
Sr 6:1 7 378 0.68
Cu 6:1 7 397 1.89
Eu 6:1 7 311 1.30
C Water
Sr 6:1 7 365 0.40
Cu 6:1 7 380 1.15
Eu 6:1 7 361 0.97
Scheme 2. Synthesis of D functionalized Merrifield resin.
710 Functional materials, 24, 4, 2017
S.V.Khimchenko et al. / New effective sorbents for purification ...
Synthesis of sorbent based on grafted D
onto Merrifield resin
Vanillin is alkylated with chloroethanol in
the presence of aqueous NaOH to yield 4-(2-hy-
droxyethoxy)-3-methoxybenzaldehyde (79%).
Then the latter is grafted onto the Merrifield
resin in the presence of NaOH in toluene. After-
wards the resulting resin is treated with meth-
anolic ammonia with adding salicylaldehyde at
reflux for 10 min. Finally, the product is filtered
out from the hot reaction mixture and washed
with methanol (Scheme 2).
2.5. Sorption studies
0.1 g of the properly prepared sorbent was
flooded with 25 ml of the solution containing
copper, strontium and europium ions in a con-
centration of 1 mg∙L–1 of each. Sorption of the
metal ions was carried out at room tempera-
ture for 30 min under magnetic stirring. The
solution was filtered through a filter paper. A
stock solution of the metal ions was used as a
reference one at atomic emission spectroscopy
measurements.
3. Results and discussion
As shown earlier, the conditions for the for-
mation of complexes with monomer as a modi-
fier and on modified silica gels vary insignifi-
cantly. That makes it possible to transfer the
optimal conditions for complexation in solutions
to the sorption mode [20]. Therefore, in order
to elucidate the compounds with most effective
ability to surface functionalisation of solid ad-
sorbents, 22 specially synthesized compounds
of class of partially hydrogenated azoloazines
were screened to their ability to form complex-
es with target metal ions. The most promising
PHHC were selected based on the optical data
of their complexes with the studied metal ions
(Table 1).
Sorption of ions depends on their charge,
size and ability to hydration. The degree of
ions sorption increases with the rise of their
valences and radiuses [21]. Table 2 shows that
the recovery rate of the metal ions on silica gel
impregnated by C and D grows in a series of
Cu2+<Sr2+<Eu3+, which corresponds to the lyotrop-
ic series for di- and trivalent cations. At sorption
of metal ions on pure silica gel, the degree of re-
Table 2. Sorption properties of the sorbents modified by PHHC
Re
ag
en
t
Co
nc
en
tr
at
io
n
of
m
et
al
io
n
in
th
e
in
iti
al
s
ol
ut
io
n,
m
g∙
L-1
Found in the solution after sorption,
mg∙L-1
Sorption degree, %
In
cr
ea
se
in
th
e
de
gr
ee
o
f r
em
ov
al
of
m
et
al
io
ns
d
ue
to
m
od
ifi
ca
tio
n
of
th
e
so
rb
en
t,
%
Sorbent
Metal ion
Impregnated by
PHHC silica gel
(ISG)
Purified
silica gel
(PSG)
ISG PSG
A
1.02 Cu2+ 0.76 0.88 25.5 13.7 11.8
1.10 Eu3+ 0.21 0.295 80.9 73.2 7.7
1.10 Sr2+ 0.945 1.06 14.1 3.6 10.5
B
0.98 Cu2+ 0.725 0.84 26.0 14.3 11.7
1.05 Eu3+ 0.12 0.26 88.6 75.2 13.4
0.99 Sr2+ 0.865 0.95 12.6 4.0 8.6
C
1.00 Cu2+ 0.305 0.860 69.5 14.0 55.5
1.10 Eu3+ 0.200 0.295 81.8 73.2 8.6
1.00 Sr2+ 0.250 0.96 75.0 4.0 71.0
D
1.00 Cu2+ 0.27 0.860 73.0 14.0 59.0
1.00 Eu3+ 0.006 0.24 99.4 76.0 23.4
1.00 Sr2+ 0.08 0.96 92.0 4.0 88.0
E
1.10 Cu2+ 0.17 0.95 84.5 13.6 70.9
1.00 Eu3+ 0.13 0.24 87.0 76.0 11.0
1.00 Sr2+ 0.26 0.96 74.0 4.0 70.0
Functional materials, 24, 34 2017 711
S.V.Khimchenko et al. / New effective sorbents for purification ...
covery grows in the series Sr2+<Cu2+< Eu3+, since
at pH ~ 7 hydroxide complexes of Cu2+ with a
radius exceeding the radius of Sr2+ are formed
in the aqueous solution. It should be noted that
for sorbents based on silica gel modified by A, B
or E, the degree of recovery falls in the region
of ions of equal valence (Sr2+<Cu2+) is observed,
which is probably due to the nature of the mod-
ifier acting as a complexing agent. In general,
we can conclude from Table 2 that modification
of silica gel significantly increases its sorption
properties. So europium, copper and strontium
degree of sorption increases by 7.7 and 23.4% (us-
ing A and D as a modifiers), 11.7 and 70.9 (us-
ing modifiers B and E) and by 8.6–88.0% (using
modifier C and D), respectively. From Table 2 it
is clear that the sorbent based on the silica gel
modified by D has a high degree of sorption of
all three target metal ions, while the sorbent
based on the silica gel modified by B has a high
selectivity for europium. Moreover, such high
values of the degree of Eu3+ and Sr2+ sorption by
silica gel modified with D (99.4% and 92% re-
spectively) make it possible to use this sorbent
for concentration the aforementioned metal
ions with initial concentrations near 1 mg∙L–1
for quantitative analysis [22].
To quantify the complexing properties of the
modifier D it was grafted onto Merrifield resin.
Since the latter is an inert carrier which does
not contribute to the sorption process, the sorp-
tion degree of Merrifild resin modified by the
compound D is determined exclusively by the
complexing properties of the modifier. As seen
from Fig. 1, the compound D has high complex-
ing properties, since the degree of sorption of
Eu3+ at its initial concentration of 1 mg∙L–1 is
85%. At the same time, the degree of sorption of
all metal ions decreases sharply with the rise of
their concentration.
The dependence of the sorbtion degree of
Cu2+ (1), Sr2+ (2), Eu3+ (3) by the sorbent modified
by the compound B from pH was investigated
in the pH range of 3.5–8.5 (Fig. 2). in accor-
Fig. 1. Concentration dependence of the degree
of sorption of Cu2+ (1), Sr2+ (2), Eu3+ (3) by Mer-
rifild resin modified by the compound D ( C is
metal ion concentration).
Fig. 2. Dependence of the degree of sorption of
metal ions by the sorbent modified by the com-
pound B on pH of the solution (1 – Sr2+, 2 – Cu2+,
3 – Eu3+).
Fig. 3. Content of the B (1) and D (2) modifiers
on silica gel surface after extraction of metal ions
from aqueous solutions with different pH values.
Fig. 4. Concentration dependence of the degree
of sorption of Cu2+ (1), Sr2+ (2), Eu3+ (3) by silica
gel, modified by the compound D from the water
solution at pH=7 ( C is metal ion concentration).
712 Functional materials, 24, 4, 2017
S.V.Khimchenko et al. / New effective sorbents for purification ...
dance with the literature data the shape of the
obtained curves is due to the nature of the cat-
ion [23]. For the non-hydrolysing Sr2+ the sorp-
tion rises with the increase of pH is observed.
For hydrolyzed ions such as Cu2+ and Eu3+, an
increase in the degree of sorption with increas-
ing pH is also observed. However, after reach-
ing the pH value coinciding with the isoelectric
point of the colloid, the value of the sorption
degree does not change further.
As seen from Fig. 2, the completeness of
the sorption of Cu2 + and Eu3 + on the sorbent
modified by compound B is achieved already at
pH ≥ 5, which makes it suitable for purification
from these metal ions of natural waters which
pH value usually varies within 6.5–8.5. In the
presence of Sr2 +, the completeness of sorption
for the sum of metal ions increases when the
pH raises to a value of 7–8. One of the disad-
vantages of non-covalently grafted sorbents is
relatively weak, compared to covalent grafted,
retention of the reagents on the matrix upon
contact with solutions [15]. Therefore there was
measured the content of the modifiers B (1) and
D (2) on the surface of silica gel after sorption
of metal ions from aqueous solutions with dif-
ferent pH values (Fig. 3). As seen from Fig. 3,
at a solution with pH near 4 about to 51% the
modifier is eluted from the silica gel surface. In
a neutral environment, only 44% of the modi-
fier is eluted from the silica gel surface. Since
the silica gel modified with B and D compounds
has high sorption properties (Table 2), it is ob-
vious that the target metal ions can bind not
only surface-fixed PHHC molecules, but also
those in the solution. Subsequently, the result-
ing complexes are sorbed on the surface of silica
gel, which ensures removal of metal ions from
the solution.
The capacity of the sorbents based on silica gel
modified by PHHC was evaluated under the opti-
Fig. 5. Concentration dependence of the degree
of sorption of Sr (1), Cu (2), Eu (3) by silica gel,
modified by the compound B from the water so-
lution at pH=7 ( C is metal ion concentration).
Fig. 6. Concentration dependence of the degree
of sorption of Sr (1), Cu (2), Eu (3) by silica gel,
modified by the compound E from the water so-
lution at pH=7 (C is metal ion concentration).
Fig. 7. Dependence of the degree of sorption of
metal ions on a sorbent based on silica gel modi-
fied by D on the modifier storage time (1 – Sr2 +,
2 – Cu2 +, 3 – Eu3+).
Fig. 8. Dependence of the degree of sorption of
Eu3+ with the concentration 1.0 mg∙L–1 by silica
gel modified by B (1) and D (2) compounds on the
total concentration of Cl–, HCO3
– and SO4
2– an-
ions. The concentration of each of the anions in
the mixture is the same.
Functional materials, 24, 34 2017 713
S.V.Khimchenko et al. / New effective sorbents for purification ...
mum value pH =7. The concentration dependenc-
es of the degree of sorption of Cu2+, Sr2+ and Eu3+
by the silica gel, modified by the compounds B,
D and E from the water solution have a similar
form (Fig.4 – 6 ). If the degree of Eu3+ sorption de-
creases insignificantly with the increase in its con-
centration from 1 to 20 mg∙L–1, a sharp drop in
the degree of Cu2 + and Sr2 + sorption is observed
in this same concentration range. Obviously,
when europium is sorbed on hybrid sorbents
based on silica gel, it is the matrix that defines
the nature of the sorption process (Table 2). On
the contrary, copper and strontium ions are
sorbed on hybrid sorbents mainly by the com-
plex-forming process with the modifiers (Fig.
1). The proposed mechanism of sorption is also
confirmed by the results of studying the aging
process of the modifier, accompanied with oxi-
dation of the phenolic fragments of the modifier
with air oxygen. As seen from Fig. 7, the degree
of Eu3+ sorption falls only by 15% when using a
sorbent stored for 360 days, while the degree of
sorption of Cu2 + and Sr2+ decreases by 30 and
80%, respectively. This phenomenon can be
useful when it is necessary to selectively extract
Eu3 + from solutions simultaneously containing
Cu2 + and Sr2 +.
The effect of 100 –1000-fold excess of extra-
neous anions Cl–, HCO3– and SO4
2– on the sorp-
tion of Eu3 + ions on silica gel modified by the
compound B and D was studied. It is seen from
Fig. 8 that the degree of sorption of Eu3+ ions on
silica gel modified by PHHC decreases slightly
with the rise of the total mineralization in the
range of 0.1– 2.0 g / L.
The result of the employing of the silica gel
modified by compound B for the separation of
the sums of metal ions from natural water con-
firms that such a sorbent is acceptable for re-
covering of microquantities of Eu3+ which has
been used as chemically identical to 241Am from
waters with low mineralization (Fig. 9).
Fig. 9. Degree of extraction of metal ions from
natural lightly mineralized water with pH = 7.0
silica gel, impregnated by B. The sorption time
is 20 min, t = 20 ° C, the sorbent mass is 0.1
4. Conclusion
Created were the sorbents based on silica
gel non-covalently modified with partially hy-
drogenated heterocyclic compounds (PHHC)
containing nitrogen as donor atoms. The most
promising PHHC were selected based on the opti-
cal data of their complexes with metal ions such
as Eu3+, Cu2+, Sr2+. The sorption properties of the
sorbents based on silica gel modified by 5 speci-
mens of PHHC were investigated. The raise of
the degree of removal of the metal ions due to
modification of the sorbent was evaluated at
their initial concentrations near 1 mg∙L–1. The
pH dependence of the degree of sorption of met-
al ions by the sorbent modified by PHHC was
investigated on the example of the compound B.
Also there were found the concentration depen-
dences of the degree of sorption of metal ions by
silica gel, modified by 3 samples of PHHC from
the water solution at pH=7. The degree of sorp-
tion of Eu3+ ions on silica gel modified by PHHC
was shown to decrease slightly with the rise of
the total mineralization in 0.1– 2.0 g / L range.
Conditions for selective sorption of Eu3+ ions
were described. The result of the application of
the silica gel modified by the compound B for
separation of the sums of metal ions from natu-
ral water confirms that such sorbent is accept-
able for recovering of microquantities of Eu3+
which has been used as chemically identical
to 241Am from waters with low mineralization.
Moreover it is shown that silica gel modified by
D is possible to use as a sorbent to concentrate
the Eu3+ and Sr2+ metal ions with initial concen-
trations near 1 mg∙L–1 for the quantitative anal-
ysis. A possible mechanism of metal ion sorp-
tion on the developed sorbents was proposed.
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