Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides
Adsorption of polyvinylpyrrolidone (PVP) and polyoxyethylene (POE) from the aqueous solutions onto surfaces of individual and mixed silicon, titanium and aluminium oxides was studied. It was found that the values of polymer adsorption depend on composition of oxides. It was shown with IR spectroscop...
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Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine
2002
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| author | Voronin, E. F. Guzenko, N. V. Gun'ko, V. M. Malysheva, M. L. Pakhlov, E. M. Eremenko, B. V. Chuiko, A. A. |
| author_facet | Voronin, E. F. Guzenko, N. V. Gun'ko, V. M. Malysheva, M. L. Pakhlov, E. M. Eremenko, B. V. Chuiko, A. A. |
| author_institution_txt_mv | [
{
"author": "E. F. Voronin",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "N. V. Guzenko",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "V. M. Gun'ko",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "M. L. Malysheva",
"institution": "National Taras Shevchenko University"
},
{
"author": "E. M. Pakhlov",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "B. V. Eremenko",
"institution": "National Taras Shevchenko University"
},
{
"author": "A. A. Chuiko",
"institution": "Інститут хімії поверхні НАН України"
}
] |
| author_sort | Voronin, E. F. |
| baseUrl_str | |
| collection | OJS |
| datestamp_date | 2018-11-27T09:42:19Z |
| description | Adsorption of polyvinylpyrrolidone (PVP) and polyoxyethylene (POE) from the aqueous solutions onto surfaces of individual and mixed silicon, titanium and aluminium oxides was studied. It was found that the values of polymer adsorption depend on composition of oxides. It was shown with IR spectroscopy that the surface of the oxides studied is fully accessible to interaction with PVP and POE. |
| first_indexed | 2025-07-22T19:30:05Z |
| format | Article |
| fulltext |
5
Surface chemistry of silica and related sorbents
ADSORPTION OF POLYVINYLPYRROLIDONE AND
POLYOXYETHYLENE WITH PURE AND MIXED SILICON,
ALUMINIUM, AND TITANIUM OXIDES
E.F. Voronin,1 N.V. Guzenko,1 V.M. Gun'ko,1 M.L. Malysheva,2
E.M. Pakhlov,1 B.V. Eremenko,2 and A.A. Chuiko1
1Institute of Surface Chemistry, National Academy of Sciences
General Naumov Str. 17, 03680 Kyiv-164, UKRAINE
2National Taras Shevchenko University
Vladimirskaya Str. 64, 02033 Kyiv, UKRAINE
Abstract
Adsorption of polyvinylpyrrolidone (PVP) and polyoxyethylene (POE) from the
aqueous solutions onto surfaces of individual and mixed silicon, titanium and aluminium
oxides was studied. It was found that the values of polymer adsorption depend on composition
of oxides. It was shown with IR spectroscopy that the surface of the oxides studied is fully
accessible to interaction with PVP and POE.
Introduction
Water-soluble non-ionogenic polymers adsorb on fumed silica surfaces due to
hydrogen bonds between electron-donating atoms of macromolecules and H atoms of silanol
groups [1]. Heteroatoms (e.g., aluminium, titanium, etc.) in the silica structure cause the
appearance of new active sites, which change the acid-base properties of the surfaces [2-6]
and thereby can affect on polymer adsorption. The aim of this work was to investigate the
influence of titania and alumina on the adsorption properties of mixed oxides based on highly
disperse silica in respect to polyvinylpyrrolidone (PVP, average molecular weight 12000
determined viscosimetrically) and polyoxyethylene (POE, average molecular weight 600000).
Such individual and mixed fumed oxides as silica A-100, A-175 and A-300; TiO2; Al2O3,
titania-silica TS-100; alumina-silicas AS-200 and AS-300 (Table) were studied by using
adsorption and infrared (IR) spectroscopy methods.
Experimental
Polymer adsorption on the oxide surfaces was determined interferometrically from the
difference in the polymer concentrations in the solution before contact with adsorbent and
after ones for 24 h [7]. The measurement was carried out at the temperature 25±0.1оС. Mass
of sorbent was equal to 500 mg, and the volume of polymer solutions was 50 ml. Adsorption
value A was evaluated according to the formula:
A = (C - Ceq) V/m SBET
6
where C and Ceq are the initial and equilibrium concentrations of the polymer respectively, V
is the volume of the solution, m and SBET denote the mass and specific surface area of
adsorbent. The SBET values of oxides differ significantly; therefore, the adsorption is shown in
mg of polymer per 1 m2 of the oxide surface.
The IR spectra of samples dried at room temperature were recorded using a Specord
M80 (Karl Zeiss) spectrophotometer. For this purpose the samples were pressed into
rectangular plates with the size of 5´22 mm and mass of 10 mg.
Results and discussion
The adsorption isotherms of polymers studied (Figs. 1-4) correspond to 2L (Langmuir
type) for PVP or 3H (high affinity) type for POE, possessing significantly larger molecular
weight compared to PVP, with different plateau adsorption. In the Langmuir equation
coordinates Сeq/А-Сeq, the adsorption isotherms are direct lines. It has allowed to determine
the maximal values of polymer adsorption Аmax for samples studied (Table). As for the
Langmuir theory, the value Аmax corresponds to the capacity of a monolayer.
There is an inverse dependence of Аmax on SBET, which is in agreement with a
reduction of the concentration of silanol groups with SBET [8, 9], while such groups are the
main adsorption sites for polar polymers, forming strong hydrogen bonds with these groups.
Table. Some characteristics of the studied oxides.
Oxide SBET,
m2/g
Oxide composition, wt.% Am, mg/m2
SiO2 Al2O3 TiO2 PVP POE
A-100 100 100 - - 1.00 0.93
А-175 175 100 - - 0.85
А-300 287 100 - - 0.68 0.65
Al2O3 140 - 100 - 0.15 0.10
AS-200 197 98 2 - 0.49 0.42
AS-300 319 89 11 - 0.50 0.27
TiO2 23 - - 100 0.73 0.50
TS-100 108 79 - 21 0.50 0.70
After introduction of titanium and aluminium oxides into a silica matrix different
aprotic acid sites also appear on a surface besides hydroxyl groups [3-5]. Therefore it would
be hypothetically possible to expect the higher sorption activity for the mixed oxides in
relation to polymers, than that in case of individual SiO2. However really the values of the
maximum adsorption of polymers studied on titania- and alumina-silicas appeared to be
lesser, than those on initial silica (Table, samples A-100 and ТS-100, A-175 and АS-200,
A-300 and АS-300).
Primary particles of studied mixed oxides consist of separate phase grains of silica and
oxides of titanium or aluminium paired with titanosiloxane or alumosiloxane bonds [10-13].
The surface of such oxides also contains silica, titania- and alumina patches. To define their
role in researched processes, the isotherms of adsorption of polymers on the surface of
individual oxides of titanium and aluminium were obtained. The value of PVP and POE
adsorption appeared to be diminished in the series of SiO2 > TiO2 > Al2O3. It is possible to
assume that it is caused by decreasing proton-donating properties of free surface OH-groups
of the specified oxides, this being testified by the shift of absorption bands of free hydroxyl
7
groups, in particular, at adsorption of diethyl ether, which amounted for SiO2 - 460,
TiO2 - 306, and Al2O3 - 270 cm-1 [14]. It is possible to conclude from given that no interaction
between electron-donating oxygen atoms of PVP or POE and surface Lewis sites occurs, and
the adsorption of polymers is caused extremely by formation of hydrogen bonds with free
hydroxyl groups. The replacement of silica surfaces by titania or alumina results in overall
decrease of polymer adsorption.
Fig. 1. Adsorption isotherms of PVP on
silicas A-300 (1), A-175 (2), A-100 (3) and
alumina-silicas AS-200 (4), AS-300 (5).
Fig. 2. Adsorption isotherms of POE on
silicas A-300 (1), A-100 (2), and
alumina-silicas AS-200 (3), AS-300 (4).
Fig. 3. Adsorption isotherms of PVP on
silica A-100 (1), TiO2 (2), and titania-silica
TS-100 (3).
Fig. 4. Adsorption isotherms of POE on
silica A-100 (1), TiO2 (2), and titania-silica
TS-100 (3).
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4
0,0
0,2
0,4
0,6
0,8
1,0
А
(m
g/
m
2 )
С
eq
(g/l)
1
2
3
4
5
0,0 0,2 0,4 0,6 0,8 1,0 1,2
0,0
0,2
0,4
0,6
0,8
1,0
А
(
m
g/
m
2 )
Сeq (g/l)
1
2
3
4
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4
0,0
0,2
0,4
0,6
0,8
1,0
А
(m
g/m
2 )
Сeq (g/l)
1
2
3
0,0 0,2 0,4 0,6 0,8 1,0 1,2
0,0
0,2
0,4
0,6
0,8
1,0
А
(m
g/m
2 )
Сeq (g/l)
1
2
3
8
In the IR spectra of individual silica and mixed oxides, there is an intensive narrow
band of free silanol groups with a maximum at 3750 cm-1 (Fig. 5, curve 1).
Fig. 5. IR spectra of silica A-300 after contact with liquid water (1) and solution
of PVP (2) and POE (3).
Fig. 6. IR spectra of samples A-100 (1) and AS-200 (2) after adsorption of POE and
of sample TS 100 after adsorption of PVP (3).
1 2 0 0 1 6 0 0 2 0 0 0 2 4 0 0 2 8 0 0 3 2 0 0 3 6 0 0 4 0 0 0
5 0
1 0 0
A
b
so
rb
a
n
c
e
(
%
)
w a v e n u m b e r ( с m - 1 )
1
2
3
1 2 0 0 1 6 0 0 2 0 0 0 2 4 0 0 2 8 0 0 3 2 0 0 3 6 0 0 4 0 0 0
5 0
1 0 0
A
b
so
rb
a
n
c
e
(
%
)
w a v e n u m b e r ( с m - 1 )
1
2
3
9
Absorption bands, which could be interpreted as IR-spectral display of surface Ti-OH or
Al-OH groups are not observed. The reasons of this effect are not clear now. It is
supposed [10] that they can be masked by bulk absorption of the various forms of sorbed
water. During adsorption of polymers the intensity of the band at 3750 cm-1 reduces and a
broad band of the disturbed OH-groups with a maximum at 3348 cm-1 appears (Fig. 5,
curve 2). It is fixed that for all silica containing samples as adsorption reaches the value Аmax
the band at 3750 cm-1 disappears completely (Figs. 5, 6), i.e. all silanol groups on the surface
of studied oxides interact with polymers. In the literature [11, 15] it is supposed that one of
the reasons of rising of the acidity of mixed oxides based on silicon dioxide is the polarisation
of silanol groups owing to inductive effect caused by the presence of heteroatoms. The fact,
the wavenumber of silanol groups at 3750 cm-1 and a value of displacement under adsorption
of polymers ~ 400 cm-1 for all the samples are the same that testifies an invariance of ºSi-OH
groups acidity. Differences in chemical and catalytic properties of individual silica and mixed
oxides on its basis [2, 5, 15] are caused, apparently, by the surface heteroatoms forming new
active sites.
Conclusion
Thus, the IR spectra testify that the investigated adsorptive processes proceed
immediately on the surface of primary particles of pyrogenic oxides, accessible not only for
interaction with rather small molecules of silanes [1, 5], but also with voluminous
macromolecules of polymers. Thus, the main mechanism of adsorption PVP and POE is the
formation of hydrogen bonds between electron-donating atoms of polymers and H atoms of
hydroxyl groups of the oxide surface even with the presence of others not only hydroxyl
active sites.
References
1. The Chemistry of Silica: Solubility, Polymerisation, Colloid and Surface Properties and
Biochemistry of Silica / Ralph K. Iler. A Wiley-Interscience Publication, New York,
1979.
2. Legrand A.P. (Ed). The Surface Properties of Silicas. Wiley, New York, 1998.
3. Tanabe K. Solids Acids and Bases. Their Catalytic Properties. - Kodansha, Tokyo,
Academic Press, New York – London, 1970.
4. Little L.H. Infrared Spectra of Adsorbed Species. - Academic Press, London, New York,
1966.
5. Kiselev A.V. and Lygin V.I. IR Spectra of Surface Compounds and Adsorbed
Substances; Nauka, Moscow, 1972 (in Russian).
6. Van Santen R.A. Theoretical Heterogeneous Catalysis. Word Scientific, Singapore, 1991.
7. Eremenko B.V., Baranchuk N.D.,and Malysheva M.L. Electro-surface properties of
silica in polyvinylpyrrolidone aqueous solutions. // Kolloid. Zh. – 1985. – V.47. –
P.678-684.
8. Sobolev V.А., Khома M.I., Оgenkо V.М., Vatamanyuk V.I., and Khaber N.V. A study of
effect of gas-phase synthesis conditions of highly dispersed silicon dioxide on their
structural characteristics. // Аdsorption and Adsorbents. – 1975. - N3. - P.79-85.
9. Mironyuk I.F., Gun'ko V.M., Turov V.V., Zarko V.I., Leboda R., and
Skubiszewska-Zieba J. Characterisation of fumed silicas and their interaction with water
and dissolved proteins // Colloid. Surf. A. – 2001. – V.180. – P.87-98.
10
10. Sushko R.V., Voronin Е.F., and Chuiko A.А. A study of highly dispersed mixed oxides
SiO2-TiO2. // Zh. Fiz. Khim. – 1979. - V.53. - P.2395-2396.
11. Lygin V.I. Structural organisation and properties of silica surface compounds from
vibratory spectroscopy and quantum chemistry. // Zh. Fiz. Khim. – 1989. - V.63. -
P.289-305.
12. Gun'ko V.M., Zarko V.I., Turov V.V., Voronin E.F., Tischenko V.A., and Chuiko A.A.
Dielectric properties and dynamic simulation of water bond to titania/silica surfaces. //
Langmuir. – 1995. – V.11. – P.2115-2122.
13. Gun'ko V.M., Zarko V.I., Chibowski E., Dudnik V.V., Leboda R., and Zaets V.A.
Structure of pyrogenic TiO2 and TiO2/SiO2 and influence of the active surface site nature
on interaction with water. // J. Colloid. Interface Sci. – 1997. – V.188. – P.39-57.
14. Kiselev A.V. and Uvarov A.V. Infrared spectra and electron spin resonance of
aluminium, silicon and titanium oxides and adsorbed substances. // Surf. Sci. – 1967. -
V.6. - P.399-421.
15. Pak V.N., Koltsov S.I., and Аleskovskii V.B. Acid site nature of titanium-containing
silica surface // Teor. Eksperim. Khim. – 1976. - V.12. - P.839-843.
16. Bremer H., Wendlandt K.P. Heterogene Katalyse; Akademie-Verlag, Berlin, 1978.
Abstract
Abstract
Experimental
Experimental
Experimental
Experimental
Results and discussion
Conclusion
References
|
| id | oai:ojs.pkp.sfu.ca:article-77 |
| institution | Surface |
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| language | English |
| last_indexed | 2025-07-22T19:30:05Z |
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| spelling | oai:ojs.pkp.sfu.ca:article-772018-11-27T09:42:19Z Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides Voronin, E. F. Guzenko, N. V. Gun'ko, V. M. Malysheva, M. L. Pakhlov, E. M. Eremenko, B. V. Chuiko, A. A. Adsorption of polyvinylpyrrolidone (PVP) and polyoxyethylene (POE) from the aqueous solutions onto surfaces of individual and mixed silicon, titanium and aluminium oxides was studied. It was found that the values of polymer adsorption depend on composition of oxides. It was shown with IR spectroscopy that the surface of the oxides studied is fully accessible to interaction with PVP and POE. Adsorption of polyvinylpyrrolidone (PVP) and polyoxyethylene (POE) from the aqueous solutions onto surfaces of individual and mixed silicon, titanium and aluminium oxides was studied. It was found that the values of polymer adsorption depend on composition of oxides. It was shown with IR spectroscopy that the surface of the oxides studied is fully accessible to interaction with PVP and POE. Adsorption of polyvinylpyrrolidone (PVP) and polyoxyethylene (POE) from the aqueous solutions onto surfaces of individual and mixed silicon, titanium and aluminium oxides was studied. It was found that the values of polymer adsorption depend on composition of oxides. It was shown with IR spectroscopy that the surface of the oxides studied is fully accessible to interaction with PVP and POE. Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine 2002-06-12 Article Article application/pdf https://surfacezbir.com.ua/index.php/surface/article/view/77 Surface; No. 7-8 (2002): Chemistry, Physics and Technology of Surface; 5-10 Поверхность; № 7-8 (2002): Химия, физика и технология поверхности; 5-10 Поверхня; № 7-8 (2002): Хімія, фізика та технологія поверхні; 5-10 3154-8091 3154-8083 en https://surfacezbir.com.ua/index.php/surface/article/view/77/75 Авторське право (c) 2001 E.F. Voronin, N.V. Guzenko, V.M. Gun'ko, M.L. Malysheva, E.M. Pakhlov, B.V. Eremenko, A.A. Chuiko |
| spellingShingle | Voronin, E. F. Guzenko, N. V. Gun'ko, V. M. Malysheva, M. L. Pakhlov, E. M. Eremenko, B. V. Chuiko, A. A. Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides |
| title | Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides |
| title_alt | Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides |
| title_full | Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides |
| title_fullStr | Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides |
| title_full_unstemmed | Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides |
| title_short | Adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides |
| title_sort | adsorption of polyvinylpyrrolidone and polyoxyethylene by pure and mixed silicon, aluminium and titanium oxides |
| url | https://surfacezbir.com.ua/index.php/surface/article/view/77 |
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