ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 1, pp. 27−30. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © J.A. Kukushkina, V.V. Sokolov, M.V. Tomkovich, 2015, published in Zhurnal Prikladnoi Khimii, 2015, Vol. 88, No. 1, pp. 31−34.
INORGANIC SYNTHESIS AND INDUSTRIAL
Effect of Nonstoichiometry of Titanium Carbide
on Porous Structure of Nanoporous Carbon
Produced from the Carbide
J. A. Kukushkina, V. V. Sokolov, and M. V. Tomkovich
Ioffe Physical-Technical Institute, Russian Academy of Sciences,
ul. Politekhnicheskaya 26, St. Petersburg, 194021 Russia
Received December 5, 2014
Abstract—It was found that the composition of nonstoichiometric titanium carbide in its homogeneity region
affects the porous structure parameters of nanoporous carbon produced by thermochemical treatment of titanium
carbide with chlorine at 800°C. It is shown that the thermochemical treatment of TiC with stoichiometric compo-
sition results in that a monodisperse microporous structure of carbon is formed, whereas a treatment of the same
kind of nonstoichiometric titanium carbide TC
yields a bidisperse micro-mesoporous structure of carbon.
The materials obtained are promising, as regards their speciﬁ c surface area and the type of the porous structure,
for application as sorbents and catalyst supports.
Titanium carbide is one of promising materials for
thermochemical treatment with chlorine in order to obtain
not only nanoporous carbon (NPC), but also titanium
chloride . The process is based on the selective removal
of titanium from the crystal lattice of titanium carbide
in the form of its chloride (TiCl
), with simultaneous
formation of NPC by the reaction
TiC + 2Cl
The boiling point of TiCl
is 136°C , which provides
its removal from the crystal lattice of TiC and from the
reaction zone, i.e., ensures the complete conversion of
TiC to C.
According to the stoichiometric relations, 3.2 kg of
and 0.2 kg of NPC can be produced from 1 kg of
TiC. Because the boiling point of TiCl
is 136°C, it can be
condensed as a liquid by using water-cooled condensers.
is of interest on its own as a raw material for
and metallic titanium . Based on this
circumstance, a waste-free technology for simultaneously
obtaining two practically important products, TiCl
NPC, can be developed on the basis of thermochemical
treatment (TCT) of titanium carbide.
The synthesis of NPC from carbides, including tita-
nium carbide, has been the subject of numerous stud-
ies [3–10]. It has been shown that the formation of the
porous structure of the NPC is strongly affected by the
kind of the chemical compound of the starting carbide,
carbide particle size, and TCT temperature. At the same
time, no attention has been given to problems associ-
ated with the effect of nonstoichiometry of the starting
carbides on the porous structure of the NPC formed in
The porous structure of NPC produced by TCT of
carbides may be strongly affected by the type of the
structure of a starting compound. Therefore, it is of interest
to study the inﬂ uence exerted by the nonstoichiometry
of titanium carbide in its TCT on the porous structure of
the NPC being formed.
Ti carbide deﬁ cient in carbon has vacancies in the
form of unoccupied interstitial positions. In fact, these are
atomic-scale “voids” in the carbide lattice and structural
constituents (empty octahedra) that can be involved in