ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 4, pp. 595−602. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © A.V. Kadomtseva, A.V. Vorotyntsev, V.M. Vorotyntsev, A.N. Petukhov, A.M. Ob’’edkov, K.V. Kremlev, B.S. Kaverin, 2015, published in
Zhurnal Prikladnoi Khimii, 2015, Vol. 88, No. 4, pp. 563−570.
At present, elementary germanium is the purest
substance. Germanium is widely used in micro- and
nanoelectronics for fabrication of pulse, parametric,
and tunnel diodes, microwave converters and in IR
engineering for fabrication of optical elements: lenses,
reﬂ ecting mirrors, windows, and lasers. High-purity
germanium doped with special impurities retains its
dominant position as one of the most promising materials
for fabrication of high-sensitivity IR photodetectors.
One of the most important practical application areas of
high-purity single-crystal germanium is the fabrication
of ionizing radiation detectors. High-purity germanium,
semiconducting germanium layers, germanium dioxide,
and fiber-optic light-emitting diodes containing
germanium are produced from its high-purity volatile
compounds, germanium tetrachloride and germanium
hydride (monogermane) .
The industry widely employs the “chloride” method
for obtaining high-purity germanium . The main
problem of the chloride technology is the low yield of
germanium (≤70%) and also the substantial loss with
chloride sewage water and the contamination of the
ﬁ nal product in the stage of hydrolysis of germanium
tetrachloride. In addition, chlorides are toxic and
corrosion-active substances, which, in turn, makes the
“chloride technology” rather labor consuming as regards
its instrumentation. Up to 70% of capital expenditure and
maintenance expenses are constituted by the expenditure
for puriﬁ cation of wastewater and efﬂ uent gases and
appreciation of equipment .
Monogermane is produced by the reaction in which
germanium tetrachloride is reduced by simple and com-
plex metal hydrides. Germanium oxide and magnesium
germanide served as germanium-containing reagents.
Lithium and potassium hydrides, lithium and sodium
borohydrides, lithium aluminohydride, and diisobutyl-
aluminum hydride  in solutions with organic solvents
and in the gas phase were used as reducing agents.
Effect of the Catalytic System Based on Multi-Walled Carbon
Nanotubes Modiﬁ ed with Copper Nanoparticles
on the Kinetics of Catalytic Reduction of Germanium
Tetrachloride by Hydrogen
A. V. Kadomtseva
, A. V. Vorotyntsev
, V. M. Vorotyntsev
A. N. Petukhov
, A. M. Ob’’edkov
, K. V. Kremlev
, and B. S. Kaverin
Nizhny Novgorod State Technical University n.a. R.E. Alekseev, ul. Minina 24, Nizhny Novgorod, 603950 Russia
Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
ul. Tropinina 49, Nizhny Novgorod, 603137 Russia
Received January 21, 2015
Abstract—Effect of a catalyst based on multi-walled carbon nanotubes modiﬁ ed with copper nanoparticles on the
kinetics of the catalytic reduction of germanium tetrachloride by hydrogen was studied in the temperature range
423–723 K. Results of experiments were used to determine the reaction order and activation energy. A mecha-
nism of the occurring reaction is suggested on the basis of the data obtained. The introduction of catalysts based
on multi-walled carbon nanotubes modiﬁ ed with copper nanoparticles made it possible to lower the reaction
temperature and achieve a germanium tetrachloride conversion of about 98%.