ISSN 1063-7745, Crystallography Reports, 2014, Vol. 59, No. 3, pp. 430–436. © Pleiades Publishing, Inc., 2014.
Original Russian Text © P.A. Demina, A.M. Zybinskii, G.M. Kuz’micheva, L.N. Obolenskaya, E.V. Savinkina, N.A. Prokudina, 2014, published in Kristallografiya, 2014, Vol. 59,
No. 3, pp. 477–483.
430
INTRODUCTION
Currently, the purification, conservation, and
regeneration of water resources are urgent problems.
This concerns all types of aqueous systems, including
natural, domestic, and industrial. In recent years,
requirements for drinking-water quality have become
more stringent. Inorganic adsorbents such as Al
2
O
3
,
SiO
2
, ZrO
2
, and TiO
2
are characterized by better
mechanical properties and higher thermal stability
than other biosorbents and organic sorbents. Among
inorganic sorbents, nanoscale titanium dioxide modi-
fications with anatase, rutile, brookite, and η-TiO
2
structures hold a particular place [1]. All modifica-
tions have a high ability of absorbing As(III) and
As(V), independent of the formal charge (rutile, broo-
kite, anatase, or η-TiO
2
) [1–3]; U(VI) (rutile) [2]; and
Bi (V) (anatase) [4] from aqueous media and a favor-
able adsorption kinetics for extracting other insoluble
metals present in aqueous systems in low concentra-
tions (Cu(II) [5], As(V) [6–8], V(V) [9], Cu(II) and
Mn(II) [10], and Cd(II) [11]). These properties
ensure rapid purification from heavy metals and/or
facilitate the reduction of their concentration to a few
micrograms per liter.
The adsorption capacity is known to depend on the
surface properties: chemical composition, physical
state, porosity, and specific surface. The unique
adsorption properties of nanoscale titanium dioxide
modifications are attributed to the formation of sur-
face hydroxyl groups with high activity at a crystallite
size (in this case, the crystallite size is equal to the
coherent scattering region) reduced to 100 Å or
smaller; it is of fundamental importance that the num-
ber of such crystallites must be close to 100% [1, 2].
These groups are self-generated when contacting
water due to the quantum-size effect on wide-gap tita-
nium dioxide semiconductors (3.2 eV for anatase,
3.0 eV for rutile, and above 3.25 eV for brookite). It
can be increased, for example, by 0.15 eV or more for
anatase at a crystallite size of 30–40 Å [1, 2]. In other
words, when the size of a titanium dioxide crystallite
decreases to a few nanometers, the physicochemical
behavior of surface atoms changes strongly due to the
variation in the ratio of the numbers of surface and
inner atoms, which is much larger in very small crys-
tallites than in micrometer-sized crystals. Note that
the properties of atoms on the crystallite surface differ
significantly from those of large crystals: the oxygen
atoms in crystallites that are adjacent to surface tita-
nium atoms are transformed to highly active hydroxyl
groups when contacting water; thus, the adsorption
properties of crystallites are much better than those of
large crystals. As was shown in [1, 2], the adsorption
properties of one large crystal are much worse than
those of several small crystallites with the same total
surface. It was suggested in [1] that the generation of
surface hydroxyl groups results from the photodecom-
position of water molecules by nanosized semicon-
ductors (by nano-TiO
2
in the case under consider-
ation).
Important factors affecting the sorption of metals is
the composition of the liquid solution phase from which
analytes are extracted (pH, ionic force, and the nature
and concentration of analytes) and the sorption con-
ditions (temperature, contact time, adsorbent mass,
etc.). The studies on the extraction of analytes onto
NANOMATERIALS,
CERAMICS
Adsorption Ability of Samples with Nanoscale Anatase
to Extract Nb(V) and Ta(V) Ions from Aqueous Media
P. A. Demina
a
, A. M. Zybinskii
a
, G. M. Kuz’micheva
a
, L. N. Obolenskaya
a
, E. V. Savinkina
a
,
and N. A. Prokudina
b
a
Moscow State University of Fine Chemical Technology, pr. Verndaskogo 86, Moscow, 119571 Russia
b
Aspect Association, pr. Vernadskogo 86, Moscow, Russia
e-mail: galina_kuzmicheva@list.ru
Received June 6, 2013
Abstract—The adsorption ability of titanium dioxide samples with nanoscale anatase prepared by the sulfate
method and Degussa (Evonik) P25, Hombfine N, and Hombikate UV-100 commercial agents with different
compositions and characteristics to extract Nb(V) and Ta(V) ions from a model aqueous system has been
investigated for the first time. It is established that the degree of sorption R (%) depends on the sorption con-
ditions and the nature of analyte. It is demonstrated that the degree of sorption of Nb(V) ions in the presence
of all samples is the highest (R
max
= 99.9%) for Degussa P25, except for the peroxide-modified samples on
which the maximum sorption of Ta(V) ions with R
max
= 99.9% has been attained.
DOI: 10.1134/S1063774514030079