Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin
The sorption of cadmium (II) cations on the surface of amorphous macroporous silicas chemically modified with β-cyclodextrin and its functional derivatives has been studied. It was shown that sorption of cadmium (II) follows the Frendlich isotherm for heterogeneous surface. Analysis of sorption kine...
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Інститут хімії поверхні ім. О.О. Чуйка НАН України
2010
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| Cite this: | Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin / L.A. Belyakova, O.M. Shvets // Хімія, фізика та технологія поверхні. — 2010. — Т. 1, № 3. — С. 274-280. — Бібліогр.: 20 назв. — англ. |
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| author | Belyakova, L.A. Shvets, O.M. |
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| citation_txt | Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin / L.A. Belyakova, O.M. Shvets // Хімія, фізика та технологія поверхні. — 2010. — Т. 1, № 3. — С. 274-280. — Бібліогр.: 20 назв. — англ. |
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| description | The sorption of cadmium (II) cations on the surface of amorphous macroporous silicas chemically modified with β-cyclodextrin and its functional derivatives has been studied. It was shown that sorption of cadmium (II) follows the Frendlich isotherm for heterogeneous surface. Analysis of sorption kinetic curves in the framework of the Lagergren kinetic model for reactions of pseudo-first and pseudo-second order shows that two parallel processes take place on the surface of β-cyclodextrin-containing silicas. It has been proved that significant increasing of cadmium (II) nitrate sorption is a result of uncharged supramolecular structures formation on the surface of silicas modified with β-cyclodextrins. The chemical composition of these supramolecular structures correlates with the polarizability of functional substituents of β-cyclodextrins.
Вивчено сорбцію катіонів кадмію (II) на поверхні аморфних макропористих кремнеземів, хімічно модифікованих β-циклодекстрином та його функціональними похідними. Показано, що сорбція кадмію (II) відповідає ізотермі Фрейндліха для гетерогенної поверхні. Аналіз кінетичних кривих сорбції у рамках кінетичної моделі Лагергрена для реакцій псевдопершого і псевдодругого порядку показує, що на поверхні β-циклодекстринвмісних кремнеземів відбувається два паралельні процеси. Доведено, що істотне збільшення сорбції нітрату кадмію (II) є результатом формування незаряджених супрамолекулярних структур на поверхні кремнеземів, модифікованих β-циклодекстринами. Хімічний склад цих супрамолекулярних структур корелює з поляризацією функціональних замісників β-циклодекстринів.
Изучена сорбция катионов кадмия (II) на поверхности аморфных макропористых кремнеземов, химически модифицированных β-циклодекстрином и его функциональными производными. Показано, что сорбция кадмия (II) соответствует изотерме Фрейндлиха для гетерогенной поверхности. Анализ кинетических кривых сорбции в рамках кинетической модели Лагергрена для реакций псевдопервого и псевдовторого порядка показывает, что на поверхности β-циклодекстринсодержащих кремнеземов осуществляется два параллельных процесса. Доказано, что существенное увеличение сорбции нитрата кадмия (II) является результатом образования незаряженных супрамолекулярных структур на поверхности кремнеземов, модифицированных β-циклодекстринами. Химический состав этих супрамолекулярных структур коррелирует с поляризуемостью функциональных заместителей β-циклодекстринов.
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Хімія, фізика та технологія поверхні. 2010. Т. 1. № 3. С. 274–280
_____________________________________________________________________________________________
* Corresponding author belyakova@isc.gov.ua
274 ХФТП 2010. Т. 1. № 3
UDC 544.723 + 547.458.68
ADSORPTION AND COMPLEXING PROPERTIES OF SILICA
MODIFIED WITH β-CYCLODEXTRIN
L.A. Belyakova*, O.M. Shvets
Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
17 General Naumov Street, Kyiv 03164, Ukraine
The sorption of cadmium (II) cations on the surface of amorphous macroporous silicas chemically
modified with β-cyclodextrin and its functional derivatives has been studied. It was shown that sorption of
cadmium (II) follows the Frendlich isotherm for heterogeneous surface. Analysis of sorption kinetic curves
in the framework of the Lagergren kinetic model for reactions of pseudo-first and pseudo-second order
shows that two parallel processes take place on the surface of β-cyclodextrin-containing silicas. It has
been proved that significant increasing of cadmium (II) nitrate sorption is a result of uncharged su-
pramolecular structures formation on the surface of silicas modified with β-cyclodextrins. The chemical
composition of these supramolecular structures correlates with the polarizability of functional substituents
of β-cyclodextrins.
INTRODUCTION
Chemical immobilization of macrocyclic or-
ganic compounds capable to form inclusion com-
plexes of "host–guest" type with ions and mole-
cules on the surface of oxide materials is a promi-
sing method for the design of active sites of extrac-
tion and concentration of impurities of toxic sub-
stances, and also for their chemical analysis in wa-
ter and other objects of environment [1–6]. Among
oxide materials highly disperse amorphous silicas
possess undoubted advantages due to not only
chemical, hydrolytic, thermal, and radiation resis-
tances, but also in-depth studied structure and reac-
tivity of its surface active centers [7–11].
The purpose of this work is to study the influ-
ence of the surface structure of β-cyclodextrin-
containing silicas on Cd (II) ions sorption from
weakly acidic solutions.
EXPERIMENTAL
Highly disperse amorphous macroporous sili-
ca– Silochrome C-120 with specific surface area
of 118 m2 g–1, average pore diameter of 40 nm,
and silanol groups concentration of 0.4 mmol g–1
was used as an initial silica adsorbent and support
in the synthesis of organosilicas.
Chemical immobilization of β-cyclodextrins
was made on the surface of Silochrome C-120
through multi-step chemical modification
(Fig. 1).
Si Si
O
Si
O
Si
O
Si
O
OH OH OH
Si Si
O
Si
O
O
Si
O
Si
O
Si
(CH2)3
NH2
OH O
Si
(CH2)3
NH2
adsorbent 1 adsorbent 2
Si Si
O
Si
O
O
Si
O
Si
O
Si
(CH2)3
NH
OH O
Si
(CH2)3
NH2
(HO)7 (OH)7
(OH)6
Si Si
O
Si
O
O
Si
O
Si
O
Si
(CH2)3
NH
OH O
Si
(CH2)3
NH2
(HO)5
(OR)6
O
O Br
9
adsorbent 3 adsorbent 4
Si Si
O
Si
O
O
Si
O
Si
O
Si
(CH2)3
NH
OH O
Si
(CH2)3
NH2
(HO)5
(OR)6
9
O
O NH NH C NH2
S
R =
SO
CH3
O
adsorbent 5
Fig. 1. Surface structure of synthesized silica ad-
sorbents
Adsorption and Complexing Properties of Silica
_____________________________________________________________________________________________
ХФТП 2010. Т. 1. № 3 275
Aminopropylsilica (adsorbent 2) was ob-
tained by interaction of hydroxylated silica (ad-
sorbent 1) with γ-aminopropyltriethoxysilane.
Organosilicas chemically modified with
β-cyclodextrin (β-СD) were synthesized by interac-
tion of aminopropylsilica with mono-
toluenesulfonyl-β-CD (adsorbent 3); bromine de-
rivative of heptakis-(toluenesulfonyl)-β-CD with
aminopropylsilica (adsorbent 4) and chemical
interaction of bromoacetyl groups of adsorbent 4
with thiosemicarbazide (adsorbent 5).
Structural and sorption parameters, chemical
composition and structure of the surface layer of
silica adsorbents (Table 1) were determined from
the isotherms of low-temperature nitrogen ad-
sorption, elemental and chemical analysis, poten-
tiometric titration, thermogravimetry data, IR,
UV, and 1H NMR spectroscopy.
Table 1. Chemical composition of surface layer of
synthesized silica adsorbents
Content of chemical elements,
%
Adsorbent
Concentration
of functional
groups of
adsorbent,
mmol g–1
H C N S Br
1 0.40 – – – – –
2 0.28 0.45 1.00 0.40 – –
3 0.035 0.70 2.80 0.40 – –
4 0.01 0.60 2.20 0.40 0.20 0.70
5 0.01 0.65 2.30 0.80 0.50 –
Sorption of Cd (II) ions was studied at 22oC
under static conditions using multi-batch method
from 2.5⋅10–4 to 4.0⋅10–3 M (pH ~ 1) Cd(NO3)2
aqueous solutions as a function of contact time
with silica and the equilibrium solution concen-
tration. Suspensions containing 0.025 g of silica
adsorbent and 20 cm3 of Cd(NO3)2 solution were
kept for 4 h in a JULABO SW22 water thermo-
stat with continuous shaking (shaking frequency
110 rpm). The amount of Cd (II) ions in the initial
and equilibrium solutions was determined by the
absorption band with λмах= 576 nm using xylenol
orange as reagent on a Perkin Elmer Lambda 35
spectrophotometer.
The relative content of various cadmium (II)
species in aqueous solutions at pH 1–5 depending
on the concentration of free NO3
– ions was calcu-
lated using the program Chemical Equilibria in
Aquatic System.
Ultraviolet absorption spectra of Cd(NO3)2
aqueous solutions were recorded on a Spe-
cord M-40 spectrophotometer in the wavelength
range 240–400 nm in quartz cells with l = 1 cm.
Infrared transmission spectra were registered
in the frequency range 4000–400 cm–1 using a
Thermo Nicolet NEXUS FT-IR spectrophotome-
ter. To record the IR spectra samples of adsorb-
ents of ~30 mg each were compacted in plates
under the pressure of 108 Pa.
RESULTS AND DISCUSSION
From aqueous solutions of cadmium nitrate
with pH ~ 1 Cd (II) ions can be adsorbed on the
surface of studied silicas as two existing species:
Cd2+ and Cd(NO3)
+, 80% of which being divalent
cation. Sorption equilibrium is achieved within
1 h, and for organosilicas 3–5 substantial sorption
capacity is already realized in the first 15 minutes
(Fig. 2). The isotherms of Cd (II) ions sorption
for all studied functional silicas are presented in
Fig. 3.
20 40 60 80 100 120
0.00
0.01
0.02
0.03
0.04
0.05
0.06
2
3
4
5
1
at / mmol g–1
t/min
.
Fig. 2. Effect of agitation time on sorption of Cd (II)
ions by silica adsorbents 1–5 (10−3 M cad-
mium (II) nitrate aqueous solution)
0.001 0.002 0.003
0
1
2
3
4
5
6
1 2
3
4
5
aeq / mmol Cd mmol–1 func. groups
Ceq/mmol ml–1
Fig. 3. Isotherms of Cd (II) cations sorption for silica
adsorbents 1–5
L.A. Belyakova, O.M. Shvets
_____________________________________________________________________________________________
276 ХФТП 2010. Т. 1. № 3
Adsorbents 1 and 2 practically do not absorb
cations Cd (II) from solutions with a concentra-
tion less than 0.001 M. The maximum sorption of
Cd (II) from 0.001 M aqueous solutions over the
content of chemically grafted β-CD at 1.1, 1.6,
and 5.2 times for adsorbents 3–5, respectively,
and the distribution coefficients increase by two
orders of magnitude in comparison with that of
initial silica (Table 2).
Table 2. Structural and sorption parameters of silica
adsorbents
Adsorbent
Specific
surface
area,
m2 g–1
Specific
sorption
of Cd (II)
cations, %
Distribution
coefficient,
L g–1
1 118 14 7
2 111 9 5
3 98 110 125
4 90 460 200
5 85 520 340
The IR spectrum of silica 1 after adsorption
of cadmium (II) is practically unchanged. In the
IR spectrum of adsorbent 2 a little shift of the
absorption band of the deformation vibrations of
the N–H bond in the primary amino groups (1571
and 1542 cm–1) into low-frequency range
(1520 cm–1) is observed, indicating the formation
of a complex between aminopropyl groups and
Cd (II) ions [12]. In the IR spectrum of adsorb-
ent 3, besides the absorption bands belonging to
the aminopropyl groups, the absorption bands of
the valence vibrations of the O–H bond for seco-
ndary alcohol groups (3375, 3290 cm–1) of β-CD
are present. At the same time, the intensity of the
valence and deformation vibrations of the C–H
bonds (2950, 2880 cm–1 and 1460, 1390 cm–1 re-
spectively) is higher than that for silica 2. After
adsorption of cadmium (II) the absorption bands
of the valence vibrations of β-CD become less
pronounced, and the absorption bands of the de-
formation vibrations of the N–H and C–H bonds
are shifted into low-frequency region (1525,
1400, and 1325 cm–1). In the IR spectrum of ad-
sorbent 4 the absorption bands of heptakis-
(toluenesulfonyl)-β-CD, namely, the bands of the
deformation vibrations of the O–H bond in the
COH groups (1365 cm–1), the valence vibrations
of the C=C bond in the benzene ring of toluene-
sulfonyl groups (1490 cm–1), the characteristic
absorption bands of the valence vibrations of the
C=O (1755 cm–1) and C–Br bonds (680 cm–1) of
the bromoacetyl groups have been registered. The
absorption band at 1455 cm–1 belongs to the de-
formation vibrations of the C–H bond, the ab-
sorption bands at 1560 and 1540 cm–1 were at-
tributed to the deformation vibrations of the N–H
bonds in the amino groups. After adsorption of
cadmium (II) the absorption bands of the valence
vibrations of the C–H bonds become less clear,
the characteristic absorption bands of the C–Br
and C=O bonds of the bromoacetyl groups are
absent; the absorption bands of the deformation
vibrations of the N–H bond are shifted in low-
frequency region (1530 cm–1). In the IR spectrum
of adsorbent 5 the absorption bands of the va-
lence vibrations of the C–H bond (2970, 2935,
2880 cm–1) of the methylene groups and the de-
formation vibrations of the O–H bond (1635 cm–1)
of the COH groups are observed. The absorption
band at 1540 cm–1 corresponds to the deformation
vibrations of the N–H bond in the amino groups,
the absorption bands at 1470 and 1435 cm–1 were
attributed to the deformation vibrations of the
amino groups and the valence vibrations of the
N–C–N and C=S bonds in thiosemicarbazide
groups. After adsorption of cadmium (II) the
absorption bands of the valence vibrations of the
N–C–N and C=S bonds disappear, and the ab-
sorption band of the deformation vibrations of
the amino groups is shifted in low-frequency
region (1520 cm–1). Hence, the side functional
groups of the upper (wider) edge of β-CD mole-
cule and its derivatives fixed on the surface of
macroporous amorphous silica participate in the
complex formation with Cd (II) ions. Increase of
sorption affinity in the series adsorb-
ent 3 < adsorbent 4 < adsorbent 5 correlates with
chelating ligands ability [13].
The interaction of β-cyclodextrin with cad-
mium (II) nitrate in a solution was studied to clari-
fy the role of the inner cavity of β-cyclodextrin in
the sorption of cadmium on organosilicas. The
electronic spectrum of cadmium (II) nitrate solu-
tion contains a symmetric absorption band with
λmax = 301 nm and ε = 710 L mol–1 cm–1 which is
assigned to n → π* transition of the N=O chro-
mophore in nitrate-ion [14]. Upon the addition of
certain amounts of β-CD to a Cd(NO3)2 solution,
the absorption band at 301 nm becomes asymmet-
ric and increases sharply in intensity
(ε = 4000 L mol–1 cm–1). Since β-CD does not
have characteristic absorption bands in the
UV region, such spectral changes of the absorp-
Adsorption and Complexing Properties of Silica
_____________________________________________________________________________________________
ХФТП 2010. Т. 1. № 3 277
tion band of chromophore N=O show the interac-
tion of NO3
– ions with β-CD, namely, the forma-
tion of inclusion complex of "host–guest" type.
Composition of inclusion compound was de-
termined by equimolar series method. The ex-
perimental data plotted in coordinates of the
Benesi-Hildebrand equation [15] fall on a straight
line for the complex of 1:1 (Fig. 4)
(CºNO3¯ ⋅ l) / D
λ = 1 / ελ + 1 / (Ks ⋅ ελ ⋅ Cºβ-CD),
where Co is initial concentration of reagents
(mol L–1); Dλ is optical density of equilibrium so-
lutions, arbitrary units (arb. u.); ελ is molar ex-
tinction coefficient of equilibrium solutions
(L mol–1 cm–1); Ks is stability constant of the
complex (L mol–1); l is thickness of absorbing
layer of analyzed solution (cm).
1000 2000 3000 4000 5000
0,000
0,001
0,002
0,003
0,004
0,005
0,006
CοNO3
− l/Dλ, mol L−1 cm
1/ Cο
β-CD, L mol−1
Fig. 4. Dependence of spectral characteristics of NO3
–
on amount of β-CD in aqueous solutions in co-
ordinates of the Benesi–Hildebrand equation for
inclusion compound of composition 1:1
The volume of inner cavity of β-CD molecule
is Vcavity β-СD = 0.262 nm3; its upper part is
V½ cavity β-CD = 0.156 nm3, the volume and diameter
of hydrated nitrate-ion are VNO3¯ = 0.153 nm3 and
d NO3¯ = 0.67 nm, respectively [16]. Consequently,
the entry of the anion into the inner cavity of β-CD
is possible only through a wider edge, and loca-
tion of NO3
– – in the top of β-CD torus. The sta-
bility constant of complex "β-CD – NO3
– " is
Ks = 1425 ± 70 L mol–1. The reason for high
strength of formed inclusion complex is that the
volumes of hydrated anion and upper part of in-
ner cavity of β-CD are virtually identical.
It has been found using chemical analysis that
the interaction product of β-CD (or its bromine-
and sulfur-containing derivatives) with Cd(NO3)2
contains not only nitrate-ions, but also Cd2+ in the
ratio [NO3
–]:[Cd2+] = 2:1. Hence, for β-CD-
containing silicas the molecular sorption of cad-
mium nitrate is observed. Chemical composition
of formed surface supramolecular compounds is
given in Table 3.
Table 3. Chemical composition of surface supra-
molecular structures
Functional groups of
β-cyclodextrins
A
ds
or
b-
en
t
type quantity
Chemical compo-
sition of supra–
molecular
structures
(elemental analysis)
3 alcohol 21 C42H70O34 ·
Cd(NO3)2
4 bromoacetyl 9 C98H112O53S6Br9 ·
4 Cd(NO3)2
5 thiosemicar-
bazide
9 C107H148O53S15N27
· 5 Cd(NO3)2
The isotherms of cadmium (II) sorption for
adsorbents 3–5 were expressed in the coordinates
of the Freundlich and Langmuir equations [17,
18]. The experimental data are well fitted to lin-
ear form of the Freundlich equation for adsorp-
tion on heterogeneous surface (Fig. 5)
log aeq = log KF + (1 / n) ⋅ log Ceq,
where aeq is equilibrium sorption (mg g–1); KF is
the Freundlich constant, sorption capacity (mg g–1);
1 / n is the Freundlich constant which character-
izes the sorption intensity; Ceq is adsorbate equi-
librium concentration in a solution (mg L–1).
-5.2 -4.8 -4.4 -4.0
-1.6
-1.2
-0.8
-0.4
0.0
5 4
log Ceq/mg · L−1
log aeq/mg · g−1
3
Fig. 5. Isotherms of Cd (II) cations sorption in the
Freundlich equation for adsorbents 3–5
The calculated Freundlich constants are given
in Table 4. The increase of the constants KF and n
in order adsorbent 3 < adsorbent 4 < adsorbent 5
is an evidence of rising contribution of side func-
tional groups of immobilized β-cyclodextrins to
L.A. Belyakova, O.M. Shvets
_____________________________________________________________________________________________
278 ХФТП 2010. Т. 1. № 3
Cd2+ sorption. Thus, the surface heterogeneity of
adsorbents 3–5 may be due to the presence of two
types of centers for sorption of Cd (II) – the inner
cavity of immobilized β-CD molecules and the
side alcohol, bromoacetyl, and thiosemicarbazide
groups (Fig. 1). It should be taken into account that
both Cd2+ and Cd(NO3)
+ ions can be adsorbed.
Table 4. Freundlich isotherm constants n and KF for
cadmium (II) cations sorption by β-cyclo-
dextrin-containing silicas at 22°С
Adsorbent n KF, mg · g–1 R2
3 0.80 3.90± 0.23 0.99
4 1.00 4.30 ± 0.26 0.99
5 1.25 5.50 ± 0.33 0.99
The Lagergren kinetic models [19] for
processes of pseudo-first order
ln (aeq – at) = ln aeq – k1t ,
where at and aeq are sorption (mg g–1) at time t and
at equilibrium, respectively (min), k1 is rate con-
stant of sorption (min–1),
and pseudo-second order
t / at = 1 / (k2 ⋅ aeq
2) + t / aeq ,
where k2 is rate constant of sorption (g⋅mg–1⋅min–1),
were used for analysis of the kinetic curves of
Cd (II) sorption. The kinetic curve (Fig. 6) for
adsorbent 3 is linear in the coordinates of the
equation for the processes of pseudo-second or-
der (the rate constant of sorption
k2 = 0.312 ± 0.019 g·mg–1⋅min–1, the correlation
coefficient R2 = 0.99).
0 20 40 60 80 100 120 140
5
10
15
20
25
30
t · at
–1
/g · mg
–1 · min–1
t/min
Fig. 6. Kinetic curve of Cd (II) cations sorption in the
Lagergren pseudo-second order equation for
adsorbent 3
It can be explained by the passing of two par-
allel reactions with substantially various rates on
the surface of adsorbent 3. This is the interaction
of cadmium cations with inner cavity of chemi-
cally fixed β-CD molecules and its side alcohol
groups. This explanation seems to be quite rea-
sonable, since the amount of adsorbed cad-
mium (II) slightly exceeds the content of grafted
β-CD (Table 2, 3). In other words, Cd (II) sorp-
tion occurs mainly with participation of inner
cavity of β-CD.
Kinetic curves for adsorbents 4 and 5 (Fig. 7)
correspond to the model of the processes of
pseudo-first order (R2 = 0.99 and k1 = 1.88 ± 0.11
and 1.97 ± 0.12 min–1, respectively).
0 10 20 30 40
-1.2
-0.6
0.0
0.6
1.2
1.8
ln (aeq− at )/1 min–1
t/min
2
1
Fig. 7. Kinetic curves of Cd (II) cations sorption in the
Lagergren pseudo-first order equation for ad-
sorbents 4 (1) and 5 (2)
It agrees well with substantial increasing of
the complex formation ability of the bromoacetyl
and thiosemicarbazide substituents in comparison
with alcohol groups [20] (Table 3). Typical
changes of IR spectra of adsorbents 1–5 after
cadmium (II) sorption confirm this conclusion.
Thus, the cadmium cations interact with side
functional groups of β-cyclodextrin chemically
grafted on the silica surface, and also with inner
cavity of β-CD (through NO3
–) forming un-
charged supramolecular structures on the surface
of silica adsorbents. Chemical composition of
these supramolecular structures correlates with
polarizability of side groups of β-CD.
CONCLUSIONS
Interaction of Cd(NO3)2 with β-CD in a solu-
tion and on the surface of highly disperse amor-
phous silicas chemically modified with β-cyclo-
Adsorption and Complexing Properties of Silica
_____________________________________________________________________________________________
ХФТП 2010. Т. 1. № 3 279
dextrin or its bromine- and sulfur-containing
functional derivatives has been studied by use of
IR and UV spectroscopy, elemental and chemi-
cal analysis, and also adsorption measurements.
It has been shown that sorption of Cd (II) fol-
lows the Freundlich isotherm for heterogeneous
surface. Analysis of sorption kinetic curves in
the framework of the Lagergren kinetic model
for the processes of pseudo-first and pseudo-
second order confirms that two parallel proc-
esses take place on the surface of β-cyclo-
dextrin-containing silicas. It has been proved
that molecular sorption of Cd(NO3)2 is attended
with the formation of supramolecular structures
on the surface of β-CD-containing silicas.
Chemical composition of these structures corre-
lates with polarizability of functional groups of
β-cyclodextrins.
ACKNOWLEDGEMENTS
The work is done at financial support of the
European Commission (grant no. ICA2-CT-
100052), and by the Ukraine National Academy
of Sciences Comprehensive Program of Funda-
mental Researches "Nanostructure Systems,
Nanomaterials, Nanotechnologies" (grant
no. N 0103U006289).
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Received 02.07.2010, accepted 17.08.2010
Адсорбційні та комплексоутворюючі властивості кремнезема,
модифікованого β-циклодекстрином
Л.О. Бєлякова, О.М. Швець
Інститут хімії поверхні ім. О.О. Чуйка Національної академії наук України
вул. Генерала Наумова 17, 03164, Київ, Україна, belyakova@isc.gov.ua
Вивчено сорбцію катіонів кадмію (II) на поверхні аморфних макропористих кремнеземів, хімічно
модифікованих β-циклодекстрином та його функціональними похідними. Показано, що сорбція кад-
мію (II) відповідає ізотермі Фрейндліха для гетерогенної поверхні. Аналіз кінетичних кривих сорбції у
рамках кінетичної моделі Лагергрена для реакцій псевдопершого і псевдодругого порядку показує, що
на поверхні β-циклодекстринвмісних кремнеземів відбувається два паралельні процеси. Доведено, що
істотне збільшення сорбції нітрату кадмію (II) є результатом формування незаряджених супрамо-
лекулярних структур на поверхні кремнеземів, модифікованих β-циклодекстринами. Хімічний склад
цих супрамолекулярних структур корелює з поляризацією функціональних замісників
β-циклодекстринів.
Адсорбционные и комплексообразующие свойства кремнезема,
модифицированного β-циклодекстрином
Л.А. Белякова, А.Н. Швец
Институт химии поверхности им. А.А. Чуйко Национальной академии наук Украины
ул. Генерала Наумова 17, 03164, Киев, Украина, belyakova@isc.gov.ua
Изучена сорбция катионов кадмия (II) на поверхности аморфных макропористых кремнеземов,
химически модифицированных β-циклодекстрином и его функциональными производными. Показано,
что сорбция кадмия (II) соответствует изотерме Фрейндлиха для гетерогенной поверхности. Анализ
кинетических кривых сорбции в рамках кинетической модели Лагергрена для реакций псевдопервого и
псевдовторого порядка показывает, что на поверхности β-циклодекстринсодержащих кремнеземов
осуществляется два параллельных процесса. Доказано, что существенное увеличение сорбции нит-
рата кадмия (II) является результатом образования незаряженных супрамолекулярных структур на
поверхности кремнеземов, модифицированных β-циклодекстринами. Химический состав этих супра-
молекулярных структур коррелирует с поляризуемостью функциональных заместителей
β-циклодекстринов.
|
| id | nasplib_isofts_kiev_ua-123456789-28992 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 2079-1704 |
| language | English |
| last_indexed | 2025-11-29T13:54:08Z |
| publishDate | 2010 |
| publisher | Інститут хімії поверхні ім. О.О. Чуйка НАН України |
| record_format | dspace |
| spelling | Belyakova, L.A. Shvets, O.M. 2011-11-27T16:55:48Z 2011-11-27T16:55:48Z 2010 Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin / L.A. Belyakova, O.M. Shvets // Хімія, фізика та технологія поверхні. — 2010. — Т. 1, № 3. — С. 274-280. — Бібліогр.: 20 назв. — англ. 2079-1704 https://nasplib.isofts.kiev.ua/handle/123456789/28992 544.723 + 547.458.68 The sorption of cadmium (II) cations on the surface of amorphous macroporous silicas chemically modified with β-cyclodextrin and its functional derivatives has been studied. It was shown that sorption of cadmium (II) follows the Frendlich isotherm for heterogeneous surface. Analysis of sorption kinetic curves in the framework of the Lagergren kinetic model for reactions of pseudo-first and pseudo-second order shows that two parallel processes take place on the surface of β-cyclodextrin-containing silicas. It has been proved that significant increasing of cadmium (II) nitrate sorption is a result of uncharged supramolecular structures formation on the surface of silicas modified with β-cyclodextrins. The chemical composition of these supramolecular structures correlates with the polarizability of functional substituents of β-cyclodextrins. Вивчено сорбцію катіонів кадмію (II) на поверхні аморфних макропористих кремнеземів, хімічно модифікованих β-циклодекстрином та його функціональними похідними. Показано, що сорбція кадмію (II) відповідає ізотермі Фрейндліха для гетерогенної поверхні. Аналіз кінетичних кривих сорбції у рамках кінетичної моделі Лагергрена для реакцій псевдопершого і псевдодругого порядку показує, що на поверхні β-циклодекстринвмісних кремнеземів відбувається два паралельні процеси. Доведено, що істотне збільшення сорбції нітрату кадмію (II) є результатом формування незаряджених супрамолекулярних структур на поверхні кремнеземів, модифікованих β-циклодекстринами. Хімічний склад цих супрамолекулярних структур корелює з поляризацією функціональних замісників β-циклодекстринів. Изучена сорбция катионов кадмия (II) на поверхности аморфных макропористых кремнеземов, химически модифицированных β-циклодекстрином и его функциональными производными. Показано, что сорбция кадмия (II) соответствует изотерме Фрейндлиха для гетерогенной поверхности. Анализ кинетических кривых сорбции в рамках кинетической модели Лагергрена для реакций псевдопервого и псевдовторого порядка показывает, что на поверхности β-циклодекстринсодержащих кремнеземов осуществляется два параллельных процесса. Доказано, что существенное увеличение сорбции нитрата кадмия (II) является результатом образования незаряженных супрамолекулярных структур на поверхности кремнеземов, модифицированных β-циклодекстринами. Химический состав этих супрамолекулярных структур коррелирует с поляризуемостью функциональных заместителей β-циклодекстринов. The work is done at financial support of the European Commission (grant no. ICA2-CT- 100052), and by the Ukraine National Academy of Sciences Comprehensive Program of Fundamental Researches "Nanostructure Systems, Nanomaterials, Nanotechnologies" (grant no. N 0103U006289). en Інститут хімії поверхні ім. О.О. Чуйка НАН України Хімія, фізика та технологія поверхні Функціоналізовані матеріали, одержані золь-гель і темплатним методами Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin Адсорбційні та комплексоутворюючі властивості кремнезема, модифікованого β-циклодекстрином Адсорбционные и комплексообразующие свойства кремнезема, модифицированного β-циклодекстрином Article published earlier |
| spellingShingle | Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin Belyakova, L.A. Shvets, O.M. Функціоналізовані матеріали, одержані золь-гель і темплатним методами |
| title | Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin |
| title_alt | Адсорбційні та комплексоутворюючі властивості кремнезема, модифікованого β-циклодекстрином Адсорбционные и комплексообразующие свойства кремнезема, модифицированного β-циклодекстрином |
| title_full | Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin |
| title_fullStr | Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin |
| title_full_unstemmed | Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin |
| title_short | Adsorption and Complexing Properties of Silica Modified with β-Cyclodextrin |
| title_sort | adsorption and complexing properties of silica modified with β-cyclodextrin |
| topic | Функціоналізовані матеріали, одержані золь-гель і темплатним методами |
| topic_facet | Функціоналізовані матеріали, одержані золь-гель і темплатним методами |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/28992 |
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