A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure
High disperse silica is used as a sorbent and carrier of medical preparations in various branches of medicine, biotechnology etc. due to its physico-chemical properties, in particular, rather developed surface, chemical inertness, considerable adsorption capacity. The protolytic equilibrium of silic...
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Інститут хімії поверхні ім. О.О. Чуйка НАН України
2017
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| Cite this: | A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure / A.A. Kravchenko, E.M. Demianenko, O.V. Filonenko, A.G. Grebenyuk, V.V. Lobanov, M.I. Terets // Поверхность. — 2017. — Вип. 9 (24). — С. 28-35. — Бібліогр.: 7 назв. — англ. |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1859825937170825216 |
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| author | Kravchenko, A.A. Demianenko, E.M. Filonenko, O.V. Grebenyuk, A.G. Lobanov, V.V. Terets, M.I. |
| author_facet | Kravchenko, A.A. Demianenko, E.M. Filonenko, O.V. Grebenyuk, A.G. Lobanov, V.V. Terets, M.I. |
| citation_txt | A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure / A.A. Kravchenko, E.M. Demianenko, O.V. Filonenko, A.G. Grebenyuk, V.V. Lobanov, M.I. Terets // Поверхность. — 2017. — Вип. 9 (24). — С. 28-35. — Бібліогр.: 7 назв. — англ. |
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| description | High disperse silica is used as a sorbent and carrier of medical preparations in various branches of medicine, biotechnology etc. due to its physico-chemical properties, in particular, rather developed surface, chemical inertness, considerable adsorption capacity. The protolytic equilibrium of silica surface is to be examined, because the structure of its hydroxylic layer determines its properties. When silicic acid is polymerized, an increase in the molecular mass of the particles formed and the acidic properties of oligomers are changed.
Высокодисперсный кремнезем благодаря своим уникальным свойствам получил широкое использование как сорбент и носитель лекарственных средств в различных областях медицины, биотехнологии и т. Для разработки новых сорбентов на основе кремнезема необходимо хорошо понимать механизмы протонного обмена, происходящие в его поверхностном гидрокси-гидратной слое на молекулярном уровне. Полуэмпирическим методом РМ7 и методом функционала плотности с использованием расширенного базового набора (6-31++G(d, p)) проведен квантовохимический анализ строения фуллереноподобных полых молекул. Рассчитаны константы диссоциации гидроксильной группы для молекул, содержащих от одного до шестидесяти кремний-кислородных тетраэдров. Обнаружено, что при постадийном увеличении количества последних в олигомеры уменьшается величина константы депротонирования силанольних групп pKa
Високодисперсний кремнезем завдяки своїм унікальним властивостям набув широкого використання як сорбент та носій лікарських засобів в різних галузях медицини, біотехнології тощо. Для розробки нових сорбентів на основі кремнезему необхідно добре розуміти механізми протонного обміну, що відбуваються в його поверхневому гідрокси-гідратному шар,і на молекулярному рівні. Напівемпіричним методом РМ7 та методом функціоналу густини з використанням розширеного базисного набору (6-31++G(d,p)) проведено квантовохімічний аналіз будови фулереноподібних порожнистих молекул. Розраховані константи дисоціації гідроксильної групи для молекул, що містять від одного до шестидесяти силіцій-кисневих тетраедрів. Виявлено, що при постадійному збільшенні кількості останніх в олігомерах зменшується величина константи депротонування силанольних груп pKa.
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| first_indexed | 2025-12-07T15:28:47Z |
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Поверхность. 2017. Вып. 9(24). С. 28–35 28
УДК 544.723
A QUANTUM CHEMICAL ANALYSIS OF DEPENDENCE OF THE
PROTOLYTIC PROPERTIES OF SILICA PRIMARY PARTICLES ON
THEIR COMPOSITION AND SPATIAL STRUCTURE
A.A. Kravchenko, E.M. Demianenko, O.V. Filonenko,
A.G. Grebenyuk, V.V. Lobanov, M.I. Terets
Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
17 General Naumov Str., Kyiv, 03164, Ukraine, E-mail: kravchenkoandrew7@gmail.com
High disperse silica is used as a sorbent and carrier of medical preparations in various
branches of medicine, biotechnology etc. due to its physico-chemical properties, in particular,
rather developed surface, chemical inertness, considerable adsorption capacity. The protolytic
equilibrium of silica surface is to be examined, because the structure of its hydroxylic layer
determines its properties. When silicic acid is polymerized, an increase in the molecular mass of
the particles formed and the acidic properties of oligomers are changed.
Keywords: density functional theory, silicic acids, fullerene-like molecules, pKa.
Intoduction
There are many synthesized silica structures nowadays, such as silica films, nanotubes,
nanospheres, nano-sized amorphous silica. They are industrially important materials widely used
in catalysis, ion exchange, chromatographic separation; they are potentially important for
synthesis of special-purpose materials. However, some physical and chemical aspects of silica
nanoparticles formation have not yet been fully explained. The structure of crystalline and
amorphous silica modifications is determined by peculiarities of the stage of formation of
primary particles. There are still some questions despite considerable progress in theoretical and
experimental study of nucleating stages. The mechanisms of primary particles condensation of
the molecular level during the process of synthesis, thermodynamic and kinetic parameters of the
stages of primary particles during that process have not yet been fully explained.
Most of silica materials are obtained by using sol-gel and hydrothermal method of
synthesis. Polycondensation of orthosilicic acid molecules is the main chemical process during
all the stages of the method, and we can write it down schematically using an equation:
≡Si–OH + ≡Si–OH ≡Si–O–Si≡ + HOH.
Experiment shows that at the initial stages of sol-gel synthesis in solution during the first
hours different oligomers are formed. The formed oligomers are as follows: dimers, linear
trimers and tetramers, cyclic trimers and tetramers, prismatic hexamers, cubic octamers and other
oligomers with more elaborated structure. The complexity in study of silicate solution and silica
solutions is different comparing to polymeric hydrocarbon compounds because of the only fact –
any change of solution (pH, T, concentration) immediately leads to the changes in the polymer
composition. Thereby, all the clearness in definition of polymer composition in solution of silicic
acid has been not yet achieved. That is why so important to study the structure and properties of
silica molecular forms which can be formed at the initial stages of synthesis.
Examination of the protolytic equilibrium at silica surface is important because the
structure of the surface hydroxylic layer determines its properties. When silicic acid is
polymerized, due to aggregation of particles with increase in their molecular masses, the acidic
properties of the oligomers formed are also changed; this work is devoted to their examination.
The reaction of deprotonation of the silanol groups can be conceived of the following
scheme:
Si–OH Si–O– +H+. (1)
29
When orthosilicic acid is polycondensed, an –O–Si(ОH)3 substitution takes place for ОН–
one of a Si–OH group differing in electronegativity. Thus, in the course of polycondensation
process, structural changes occur in newly formed oligomers capable to affect their acidic
properties.
Computational methods
All the calculations have been carried out by semiempirical PM7 method as well as by
density functional theory method (DFT) with exchange-correlation functonal B3LYP and
valence-split basis set 6-31++G(d,p). The effect of aqueous medium was taken into account
within the frameworks of a continual solvent model (РСМ). All the computations have been
realized by means of program packages US GAMESS [1] and MOPAC [2]. The deprotonation
constant рKа2 has been evaluated by the formula: рKа= ΔGreact./2.303RT, where R – universal gas
constant, Т – temperature, and ΔGreact – the Gibbs free energy of the deprotonation reaction.
Results and discussion
In [3] dissociation of orthosilicic acid molecule in aqueous solutions was examined by
Hartree-Fock-Roothaan method as well as by density functional theory with functionals В3LYP
and M06-2x and within the frameworks of Møller-Plesset second order perturbation theory with
basis set 6-311++G(d,p). The thermodynamic and kinetic characteristics of the reaction of proton
transfer from orthosiicic molecule to a water molecule of the hydrate cover have been calculated
as well as the equilibrium constant (рKа) of this process. The the dissociation constant estimated
from the calculations by DFT method with taking solvent effect into account (PCM) (рKа = 9.5)
have been shown to be the best fit to the experimental one in aqueous solutions (9.46). In [4] a
quantum chemical analysis of the structures of the molecules of silicic acid oligomers was made
by DFT method with use of expanded basis set (6-31++G(d,p)) and the pKa values were
computed for clusters including one to eight silicon-oxygen tetrahedra. The step-by-step increase
in the number of tetrahedra in oliugomers has been found to decrease the value of the
deprotonation constants (pKa) of silanol groups. The authors of [5] calculated 29Si NMR spectra
of fullerene-like hollow oligomers of silicic acid consisting of 1, 2, 4, 8, 10, and 20 silicon-
oxygen tetrahedra by DFT method with hybride exchange-correlation functional B3LYP and
basis set 6-311+G(2d, p) with use of GIAO procedure.
This work is devoted to the examination of the protolytic properties of fullerene-like
hollow oligomers as dependent on their dimensions and should be considered as a logical
continuation of the article [4] (with increasing the number of silicon-oxygen tetrahedra in the
models up to 60).
High disperse silica has a rather complicated structure. The primary particles with size of
5-100 nm are built of protoparticles with size of less than 1 nm. In their turn, primary particles
form agglomerates of aggregates with sizes of 1-50 μm [6]. A question arises, how can we
simulate a silica particle. The HRTEM images of individual fumed oxides are shown in Fig. 1 а.
The structure of a primary particle one can mimic by use of various composition of fullerene-like
molecules as protoparticles. Thus, a model of primary particle is shown in Fig.1, b consisting of
seven fullerene-like molecules Si60O90(OH)60. According to the structural features of high-
disperse silica, a set can be used of various size fullerene-like molecules with different structural
and protolytic properties as a model for protoparticles.
30
A b
Fig. 1. HRTEM images of individual fumed oxides (a) A-300 [7] and model for primary
particle built of fullerene-like species Si60O120(OH)60 (b).
Fullerene-like molecules SinO1,5n(OH)n are structural analogues of carbon fullerenes where
carbon atoms are substituted by tetrahedra SiO3(OH). In Fig. 2 fullerene-like molecules are
shown consisting of 10, 20, 24 and 60 silicon-oxygen tetrahedra.
Aa b
c d
Fig. 2. Equilibrium structures of fullerene-like molecules: a – Si10O12(OH)16, b - Si20O30(OH)20,
c - Si24O36(OH)24, d – Si60O90(OH)60.
31
Besides the number of silicon-oxygen tetrahedra, the molecules mentioned differ also in the
structural features of their arrangement. Thus, Si10O12(OH)16 molecule is a cell with adamantane
structure, in Si20O40(OH)20 molecule tetrahedra form only pentagons whereas in Si24O36(OH)24
molecule, besides pentagons, there are two opposite hexagons. In Si60O90(OH)60 molecule
silicon-oxygen tetrahedra form hexagons arranged around a pentagon. In order to understand the
effect of structure and composition on the protolytic properties of silanol groups, a comparative
analysis has been carried out of the changes in atomic charges of a ≡Si–OH group as wellas in
the Si–O and O–H bond lengths with increasing molecular sizes. As our computational
possibilities give no opportunity to compare the parameters mentioned by means of density
functional theory method, for calculations semiempirical PM7 method was used.
Simulation of the protolytic equiibrium of the silanol groups of silicic acid oligomers was
realized with use of two systems of the same composition as models differing as follows: in the
first one, a silanol group was surroubded by a cluster of water molecules (Fig. 3 a), in the second
one the proton of silanol group was separated from its oxygen atom for about 4 Å (Fig. 3 b).
When optimizing the structures of these systems, a potential barrier was localized between them
and hydronium cation was formed in the second system due to the proton transfer within the
chain of water molecules: SiO–···H2O···H2O···+H3O. In such a way charge-separation complexes
were obtained on the silanol groups of all the oligomers studied.
Aa b
Fig. 3. Equilibrium structures of a Si20O30(OH)20 molecule interacting with seven water
molecules in the molecular state (a) and in the carge-separated state (b).
The changes in the atomic charges of hydrogen, oxygen, and silicon of silanol group as well
as in the Si–O and О–Н bond lengths with increasing number of atoms in the molecule have a
complicated character but as a whole, show a similar tendency to changes. When the number of
silicon-oxygen tetrahedra in the molecules increases, an increase in atomic charges takes place
on hydrogen, oxygen, and silicon (Fig. 4, a, b, c). Simultaneously the Si–O bond length increases
and the О–Н bond length decreases (Fig. 4, d, i). The changes in calculated pKa values are
32
irregular and, as a whole, manifest a tendency to a decrease with increasing molecular sizes (Fig.
4, f).
Fig. 4. Plots of hydrogen (a), oxygen (b) and silicon (c) atomic net charges, of О-Н (d) and Si-O
(i) bond lengths as well as of рKa values (f) on the number of silicon atoms in the
molecules.
The value of Gibbs free energy for deprotonation decreases from orthosilicic acid to
disilicic acid, then increases for the trimer, then decreases once more for the complexes with
tetramer Si4O13H10 and pentamer Si5O14H12. Those values found by PM7 method agree well with
findings by DFT method. The deprotonation constants for silanol groups (pKa) change symbately
to the changes in the free Gibbs energy and, as a whole, decrease with an increase in the
polymerization degree.
33
Аa b
Fig. 5. Equilibrium structures of a pair of Si24O36(OH)24 molecules interacting with seven water
molecules in the molecular state (a) and in charge-separated (b)
The calculated рKа value for the complex built by two Si24O36(OH)24 molecules contacting
via hydrogen bonds by faces formed by six silicon-oxygen tetrahedra is equal to 11.8. The net
charge on the silicon atom of the silanol group contacting with water molecules is equal to 0.89
whereas those on the oxygen atom and on the hydrogen atom are equal to –0.70 and 0.41
respectively. The рKа value for the complex of three Si24O36(OH)24 molecules is equal to 3.8.
It should be noted that taking into account the effect of solvent decreases the pKa value.
Thus, the calculated solvent-free finding for the complex including 60 silicon atoms is equal to
12.2 whereas analogous value accepting solvent effect equals to 8.3.
The calculated pKa values for the complex of two Si60O90(OH)60 molecules without solvent
effect is equal to 3.3.
Conclusion
Starting from the results of calculations of the equilibrium structural and enegy parameters
of the hydrated complexes of silicic acids, one can assert that a step-by-step increase in the
number of silicon-oxygen parameters in the oligomer results in shortening of interatomic bonds
and in changes of atomic net charges what is reflected in a decrease in the value of deprotonation
of silanol groups pKa. In turn, an increase in the number of contacting molecules leads to the
growth in of pKa value. The accordance of the calculated deprotonation constants of silanol
groups as dependent on the of polycondemsation of silicic acid with respective experimental data
support a probability of use of the complexes considered for simulation of the deprotonation-
protonation processes occuring on silica surface.
34
References
1. Schmidt M.W., Baldridge K.K., Boatz J.A. et al. General atomic and molecular electronic-
structure system: Review // J. Comput. Chem., 14 (1993) 1347.
2. Stewart J.J.P. MOPAC 2012, Colorado Springs, CO, Stewart Computational Chemistry,
USA, http://openmopac.net/, 2014.
3. Demianenko E., Ilchenko M., Grebenyuk A., Lobanov V. A theoretical study on orthosilicic
acid dissociation in water clusters, Chem. Phys. Lett., 515 (2011) 274.
4. Кравченко А.А., Демяненко Є.М., Гребенюк А.Г., Лобанов В.В. Квантовохімічне
моделювання протолітичної рівноваги поверхні кремнезему. Хімія, фізика та
технологія поверхні, 5 (2014) 16.
5. Filonenko O.V., Kuts V.S., Terebinska M.I., Lobanov V.V. Quantumchemical calculation of
29Si-NMR spectrum of silicon dioxide fullerene-like molecules, Chemistry, Physics and
Technology of Surface, 6 (2015) 263.
6. Кластеризация воды и пути ее использования, В.В. Туров, В.М. Гунько. – Киев:
Наукова думка, 2011. – 314 с.
7. V.M. Gun’ko, V.I. Zarko , O.V. Goncharuk et al. Nature and morphology of fumed oxides
and features of interfacial Phenomena, Applied Surface Science, 366 (2016) 410–423.
КВАНТОВОХІМІЧНИЙ АНАЛІЗ ПРОТОЛІТИЧНИХ
ВЛАСТИВОСТЕЙ ПЕРВИННИХ ЧАСТИНОК КРЕМНЕЗЕМУ
ВІД ЇХНЬОГО СКЛАДУ ТА ПРОСТОРОВОЇ БУДОВИ
Кравченко А.А., Дем’яненко Є.М., О.В. Філоненко, Гребенюк А.Г.,
Лобанов В.В., М.І. Терець
Інститут хімії поверхні ім. О.О. Чуйка Національної академії наук України,
вул. Генерала Наумова, 17, Київ, 03164, Україна
Високодисперсний кремнезем завдяки своїм унікальним властивостям набув широкого
використання як сорбент та носій лікарських засобів в різних галузях медицини, біотехнології
тощо. Для розробки нових сорбентів на основі кремнезему необхідно добре розуміти механізми
протонного обміну, що відбуваються в його поверхневому гідрокси-гідратному шар,і на
молекулярному рівні. Напівемпіричним методом РМ7 та методом функціоналу густини з
використанням розширеного базисного набору (6-31++G(d,p)) проведено квантовохімічний аналіз
будови фулереноподібних порожнистих молекул. Розраховані константи дисоціації гідроксильної
групи для молекул, що містять від одного до шестидесяти силіцій-кисневих тетраедрів.
Виявлено, що при постадійному збільшенні кількості останніх в олігомерах зменшується величина
константи депротонування силанольних груп pKa.
35
КВАНТОВОХИМИЧЕСКИЙ АНАЛИЗ ПРОТОЛИТИЧЕСКИХ
СВОЙСТВ ПЕРВИЧНЫХ ЧАСТИЦ КРЕМНЕЗЕМА ОТ
ИХНЕГО СОСТАВА И ПРОСТРАНСТВЕННОГО СТРОЕНИЯ
Кравченко А.А., Демьяненко Е.М., О.В. Филоненко, Гребенюк А.Г.,
Лобанов В.В., Терець М.И.
Институт химии поверхности им. А.А. Чуйко Национальной академии наук Украины,
ул. Генерала Наумова, 17, Киев, 03164, Украина
Высокодисперсный кремнезем благодаря своим уникальным свойствам получил широкое
использование как сорбент и носитель лекарственных средств в различных областях медицины,
биотехнологии и т. Для разработки новых сорбентов на основе кремнезема необходимо хорошо
понимать механизмы протонного обмена, происходящие в его поверхностном гидрокси-
гидратной слое на молекулярном уровне. Полуэмпирическим методом РМ7 и методом
функционала плотности с использованием расширенного базового набора (6-31++G(d, p))
проведен квантовохимический анализ строения фуллереноподобных полых молекул. Рассчитаны
константы диссоциации гидроксильной группы для молекул, содержащих от одного до
шестидесяти кремний-кислородных тетраэдров. Обнаружено, что при постадийном увеличении
количества последних в олигомеры уменьшается величина константы депротонирования
силанольних групп pKa.
|
| id | nasplib_isofts_kiev_ua-123456789-148530 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 2617-5975 |
| language | English |
| last_indexed | 2025-12-07T15:28:47Z |
| publishDate | 2017 |
| publisher | Інститут хімії поверхні ім. О.О. Чуйка НАН України |
| record_format | dspace |
| spelling | Kravchenko, A.A. Demianenko, E.M. Filonenko, O.V. Grebenyuk, A.G. Lobanov, V.V. Terets, M.I. 2019-02-18T14:47:20Z 2019-02-18T14:47:20Z 2017 A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure / A.A. Kravchenko, E.M. Demianenko, O.V. Filonenko, A.G. Grebenyuk, V.V. Lobanov, M.I. Terets // Поверхность. — 2017. — Вип. 9 (24). — С. 28-35. — Бібліогр.: 7 назв. — англ. 2617-5975 https://nasplib.isofts.kiev.ua/handle/123456789/148530 544.723 High disperse silica is used as a sorbent and carrier of medical preparations in various branches of medicine, biotechnology etc. due to its physico-chemical properties, in particular, rather developed surface, chemical inertness, considerable adsorption capacity. The protolytic equilibrium of silica surface is to be examined, because the structure of its hydroxylic layer determines its properties. When silicic acid is polymerized, an increase in the molecular mass of the particles formed and the acidic properties of oligomers are changed. Высокодисперсный кремнезем благодаря своим уникальным свойствам получил широкое использование как сорбент и носитель лекарственных средств в различных областях медицины, биотехнологии и т. Для разработки новых сорбентов на основе кремнезема необходимо хорошо понимать механизмы протонного обмена, происходящие в его поверхностном гидрокси-гидратной слое на молекулярном уровне. Полуэмпирическим методом РМ7 и методом функционала плотности с использованием расширенного базового набора (6-31++G(d, p)) проведен квантовохимический анализ строения фуллереноподобных полых молекул. Рассчитаны константы диссоциации гидроксильной группы для молекул, содержащих от одного до шестидесяти кремний-кислородных тетраэдров. Обнаружено, что при постадийном увеличении количества последних в олигомеры уменьшается величина константы депротонирования силанольних групп pKa Високодисперсний кремнезем завдяки своїм унікальним властивостям набув широкого використання як сорбент та носій лікарських засобів в різних галузях медицини, біотехнології тощо. Для розробки нових сорбентів на основі кремнезему необхідно добре розуміти механізми протонного обміну, що відбуваються в його поверхневому гідрокси-гідратному шар,і на молекулярному рівні. Напівемпіричним методом РМ7 та методом функціоналу густини з використанням розширеного базисного набору (6-31++G(d,p)) проведено квантовохімічний аналіз будови фулереноподібних порожнистих молекул. Розраховані константи дисоціації гідроксильної групи для молекул, що містять від одного до шестидесяти силіцій-кисневих тетраедрів. Виявлено, що при постадійному збільшенні кількості останніх в олігомерах зменшується величина константи депротонування силанольних груп pKa. en Інститут хімії поверхні ім. О.О. Чуйка НАН України Поверхность Теория химического строения и реакционной способности поверхности. Моделирование процессов на поверхности A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure Квантовохимический анализ протолитических свойств первичных частиц кремнезема от ихнего состава и пространственного строения Квантовохімічний аналіз протолітичних властивостей первинних частинок кремнезему від їхнього складу та просторової будови Article published earlier |
| spellingShingle | A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure Kravchenko, A.A. Demianenko, E.M. Filonenko, O.V. Grebenyuk, A.G. Lobanov, V.V. Terets, M.I. Теория химического строения и реакционной способности поверхности. Моделирование процессов на поверхности |
| title | A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure |
| title_alt | Квантовохимический анализ протолитических свойств первичных частиц кремнезема от ихнего состава и пространственного строения Квантовохімічний аналіз протолітичних властивостей первинних частинок кремнезему від їхнього складу та просторової будови |
| title_full | A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure |
| title_fullStr | A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure |
| title_full_unstemmed | A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure |
| title_short | A quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure |
| title_sort | quantum chemical analysis of dependence of the protolytic properties of silica primary particles on their composition and spatial structure |
| topic | Теория химического строения и реакционной способности поверхности. Моделирование процессов на поверхности |
| topic_facet | Теория химического строения и реакционной способности поверхности. Моделирование процессов на поверхности |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/148530 |
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