The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes

Abstract

In this article were generalized publications for 20-30 years. The properties of the modern electrochemical methods for obtaining rhenium and its alloys had been given. More than 100 scientific works for rhenium obtaining and its alloys were analyzed. In the reviewed article has been shown that rhenium more often deposited from sulfate, phosphoric acid, ammonium sulphate, citrate, alkaline and other electrolytes. The property of electrodeposition rhenium with metals (Ni, Co, Fe, W, Zn, Cr, Pt, Pd, Rh, Au, Ag, Cu, Se, S, Te and so on) has been shown. The electrolyte composition and terms regime of electrolysis for obtaining these alloys rhenium from different electrolytes had been given. With using potentiostatic, voltamperic, temperature and kinetic methods was estimated kinetic and mechanism of mutual electrodeposition rhenium with different metals. In the review were estimated scientific base of regularity for mutual electrodeposition rhenium with chalcogenides from different electrolytes and synthesized new semi-conductive covers of rhenium chalcogenides by using different electrochemical ways. As electrolyte were used sulphate, teasulphate, chloride sulphate, chloride borate, alkaline liquids, containing different concentrations of rhenium and chalcogenides (S, Se, Te). Analysis of results for measures cathodic and anodic polarization curves for mutual electrodeposition rhenium with chalcogenides (S, Se, Te) has been shown, that the process accompanied depolarization, which proves the formation of a chemical compound or solid solution on the base these compounds and estimates potential areas for which on the cathode obtain compounds stoichiometric composition. In the review the works concern electrodeposition triple alloys of rhenium with different metals were given. All chalcogenodes rhenium are semi-conductive ma terials as has been estimated.

Full text

J. Chem. Eng. Chem. Res.
Vol. 1, No. 3, 2014, pp. 185-198
Received: June 19, 2014; Published: September 25, 2014
Journal of
Chemical Engineering
and Chemistry Research
The Electrochemical Deposition of Rhenium
Chalcogenides from Different Electrolytes
Elza Salakhova
Institute of Catalysis and Inorganic Chemistry of the Azerbaijan National Academy of Sciences, 113, H.Javid av., Baku, Dpt.
Electrodeposition Rhenium Alloys, Azerbaijan
Corresponding author: Elza Salakhova (elza_salahova@mail.ru)
Abstract: In this article were generalized publications for 20-30 years. The properties of the modern electrochemical methods for
obtaining rhenium and its alloys had been given. More than 100 scientific works for rhenium obtaining and its alloys were analyzed.
In the reviewed article has been shown that rhenium more often deposited from sulfate, phosphoric acid, ammonium sulphate, citrate,
alkaline and other electrolytes. The property of electrodeposition rhenium with metals (Ni, Co, Fe, W, Zn, Cr, Pt, Pd, Rh, Au, Ag, Cu,
Se, S, Te and so on) has been shown. The electrolyte composition and terms regime of electrolysis for obtaining these alloys rhenium
from different electrolytes had been given. With using potentiostatic, voltamperic, temperature and kinetic methods was estimated
kinetic and mechanism of mutual electrodeposition rhenium with different metals. In the review were estimated scientific base of
regularity for mutual electrodeposition rhenium with chalcogenides from different electrolytes and synthesized new semi-conductive
covers of rhenium chalcogenides by using different electrochemical ways. As electrolyte were used sulphate, teasulphate, chloride
sulphate, chloride borate, alkaline liquids, containing different concentrations of rhenium and chalcogenides (S, Se, Te). Analysis of
results for measures cathodic and anodic polarization curves for mutual electrodeposition rhenium with chalcogenides (S, Se, Te) has
been shown, that the process accompanied depolarization, which proves the formation of a chemical compound or solid solution on
the base these compounds and estimates potential areas for which on the cathode obtain compounds stoichiometric composition. In
the review the works concern electrodeposition triple alloys of rhenium with different metals were given. All chalcogenodes rhenium
are semi-conductive ma terials as has been estimated.
Key words: Electrochemistry, thin films, rhenium chalcogenides, rhenium alloys.
1. Introduction
The authors of present work concentrated their
efforts on rhenium and its alloys. This metal has some
specific properties and finds its application in various
fields of semi-conducting industry. In recent years a
sphere of using these compounds was substantially
widened space technique, electronics, IT sector and so
on. There was also emerged a necessity to investigate
their physical and chemical properties and to elaborate
effective technology of getting alloys basing on these
elements. There are some works and patents
describing methods of obtaining rhenium shining
metallic sediments cited in the references [1-40].
Substantial mechanical strength, hardness, high
electrical impedance and other properties of rhenium
alloy rhenium and its alloys to be widely used in
various fields of technique. Alloys of rhenium with a
range of metals are used in electronic, electrometrical
and atomic technique as well for production of special
coatings [1-9].
There are various methods for obtaining thin films
of rhenium semi-conducting alloys. But the analysis
of known methods of obtaining rhenium
chalcogenides’ thin films showed that the most
perspective and less expensive is electrochemical
method which has those advantages, that it does not
need sophisticated equipment, high temperatures and
allows to produce an alloy of high purity. Using this
method it is easy to control thickness, a composition
of a coating, and, varying electrolysis regime, to get

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
186
coatings with demanded composition[14, 15] The
purpose of this paper is to summarize, organize and
view publications for 20-30 years and to identify
trends and opportunities of modern electrochemical
methods (voltammetry, potentiometry, ammeter, etc.)
for producing rhenium alloys. The survey provided
more than 100 works devoted to the preparation of
rhenium alloys by electrochemical method. Review
article also includes the new works on
electrodeposition of chalcogenide rhenium by the
electrochemical method from different electrolytes.
The present work was made aiming to research the
appropriate processes, to determine scientific base of
electro-deposition of rhenium chalcogenides and to
define physicochemical properties of produced thin
films. The electrodeposition of metals is one of the
main sections of electrochemistry having great
practical importance. Sphere of application of
electrolytic metals constantly widens due to rapid
growth of technique. Nowadays it is hard to name a
field where electrolytic metals and alloys are not
presented.
2. Electrodeposition of Rhenium and Its
Alloys
The electrodeposition of metals is carried out both
from water solutions and non-water organic and melts
environments. Main regularities of electrodeposition
of metals from water and organic environment do not
differ substantially. But it is possible to deposit from
melted environment those metals which do not
separate from water solutions (vanadium,
molybdenum, tungsten, zirconium and other). Metallic
rhenium and it’s alloys have unique physico-chemical
properties, due to winch find wide application in the
most important fields of modern technique [1-10].
Rhenium alloys with metals of platinum group can be
used for production of electric contacts having high
operational properties. Distinctive property of rhenium
is its resistance to electro-corrosion that prevents
burning of contacts.
Further is opening a new field for application of
rhenium-oil refining industry, in which rhenium in
combination with platinum is used as catalyst in oil
reforming processes for production of high octane
benzenes. The application of rhenium-platinum
catalysts prolongs a life period of catalyst five times
and raises the process effectiveness more than by 60%.
Simultaneously the octane number of produced
benzene rose to 100-105 units. Thus the application of
catalysts of mentioned type provided a new quality
jump in oil refinery. Thin coatings of rhenium
disulphide were offered as catalyst for alcohols
dehydrogenization process. Mostly interested are new
reports about works in the field of application of
rhenium and its alloys for needs of air- and rocket
industry. Not less interesting and important may be
considered the application of rhenium in nuclear
technique [7, 11]. The rising consumption of rhenium
stimulates a searching of new sources of raw, effective
methods of its refining, development of new methods
of production of rhenium and its alloys.
Hot sulfuric acid reacts with rhenium, transforming
it to HReO4. Rather easily rhenium dilutes in bromine
water at slight heating. Rhenium vigorously reacts
with halogens. It forms simple and complex
halogenides and oxyhalogenides. Rhenium
halogenides present interest for technologies and
analytical chemistry, because they are volatile. The
purification of metallic rhenium from impurities by
the method of rhenium purification after its
chlorination is based mostly on volatility of rhenium
chlorides.
Rhenium reacts with sulphur, selenium, tellurium
and forms sulfides, selenides and tellurides [2]. With
selenium rhenium forms following compounds:
Re2Se7, ReSe2, ReSe, Re3Se2. In rhenium-sulfur
system there was defined occurring of rhenium
sulfides ReS, Re2S2, ReS2, Re2S5, ReS3 and Re2S7.
Rhenium sulfides and selenides are effective catalysts
for hydration of organic materials. Their advantages in
comparison with metallic catalysts of platinum group

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
187
consist of that they are not poisoned by sulfur
containing compounds. Rhenium sulfides also
catalyze redox reactions of NO and N2O at the
temperature of 100 °C. Besides mentioned fields of
application rhenium can be used in analytical
chemistry (as a reagent for potassium, for fractured
crystallization of rare earth metals as it is generally
known [3-10], rhenium is deposited from sulfuric,
ammonium-sulfuric, phosphatic, oxalic, citric, alkaline
and other electrolytes. The investigation of the
process of electrodeposition of rhenium, one of trace
chemical elements, has practical and theoretical
interest [1-5, 8-10, 21].
The group of Chilian scientists studied rhenium and
rhenium oxides being obtained by electrodeposition
from alkaline perrhenate electrolyte in a standard
electrochemical cell (cathode and anode). The Cu
substrate was used as the cathode, with an apparent
surface area of 13 mm2, whereas the Pt electrode was
the anode, with an apparent surface area of 1 cm2. The
galvanostatic electrodeposition was conducted with a
5 A-30 V GW rectifier (model GPC-3030D), which
also allowed cell voltage measurement. Regarding
rhenium and rhenium oxide electrodeposition was
related to the use of an aqueous acidic electrolyte
(NH4ReO4 or HReO4 dissolved in H2SO4) and in some
cases preparing and electrolyte by dissolving metallic
Re in hydrogen peroxide. The authors found that on
the zone near the edge of the dendrite of the
electrodeposited material, it is possible to ascertain
that the mechanism of electro crystallization involves
the reduction of Re (7+) from the ReO4¯ ions to
metallic Re (0) throughout the successive reduction of
ReO3 (6+) to ReO2 (4+). It is possible to
electrodeposit rhenium rhenium and rhenium oxides
from alkaline aqueous electrolyte without evident
formation of powdery deposits [24].
In the works [25, 26] there were synthesized and
studied electrochemical and photophysical properties
of a thin coating of Rhenium.
In the monograph [27] the methods of extraction of
rhenium from raw and secondary materials, obtaining
metallic rhenium and products from it are described.
Special attention was paid to extraction-sorption
processes, having dominating position in rhenium
metallurgy. Specific examples of existing
technological schemes of rhenium extaction from
various kinds of materials and their equipment design
[27] are given.
In Uruguay the comparative study of
electrochemical and optical properties of rhenium
deposited on gold and platinum was carried out [28].
Rhenium-containing films were grown on gold and
platinum after different potentiostatic and
potentiodynamic polarizations in the 0.20 V to 0.70 V
range (vs rhe) in aqueous acid perrhenate
The method [29] involves placing the stent in a
series of rinsing and electroplating solutions, one
containing radioactive rhenium (186Re, 188Re, or
both).The overall processing time is 15 min and the
procedure may be conveniently applied just prior to
the stent insertion. The plated stent contains
radioactive rhenium in a 1.2 microm-thick cobalt layer,
with an outer 2 microm layer of gold.
Electrochemical oxidation of silver and rhenium
electrodes in molten LiF-NaF-KF eutectic at 600 °C
was investigated by cyclic and convolutional
voltammetry [30].
Yakovlev M.A. [31] studied modeling and
optimization of the processes of extraction of rhenium
from multi-component alloys. It was defined that
when anodic dissolving alloys on the base of nickel,
rhenium, nickel, cobalt, aluminum and chrome
practically fully go into solution, tungsten and
molybdenum go as tungsten and molybdenum acids
and tantalum and niobium go to sludge.
L.G. Holz [32] in the PH.D thesis named “The
voltammetric determination of rhenium in raw and
anthropogenic materials” for the first time determined
and interpreted peaks, observed on anodic and
cathodic voltammetric curves in the processes of

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
188
electrochemical transforming of perrhenate ions in
acidic electrolyte background on graphite electrod for
the first time he proposed to make the calculation of
the concentration of perrhenate ions by stripping
voltammetry (SVA) method not by current peak but
by total area under electropositive peaks depending on
ions concentration in the solution. The scientists from
Hungarian Academy of Sciences have shown that the
chemical nature of electrodeposited rhenium species
depends on the H2SO4 concentration in the supporting
electrolyte from which the deposition takes place [33].
A smooth Au electrode with about apparent surface
was used as a working electrode. In order to eliminate
impurities and traces of rhenium, the gold electrode
was an one with about 0.5 A for 10 -15 s in 0.5 M
H2SO4.
In the co-operative work of Chilian and Spainian
researchers rhenium thin films were prepared by
electrodeposition from an aqueous solution containing
0.1 M Na2SO4+ H2SO4, pH 2 in presence of y mM
HReO4 [34].
In Tel-Aviv University, Israel, there was carried out
the electrodeposition of rhenium tin nano-wires [35].
The effects of bath composition 34 mM NH4ReO4,
12-93 mM SnCl2, 12-93 mM Mg(SO3NH2)2·H2O, and
343 mM H3C6H5O7 (citric acid, anhydrous) of
operative conditions were investigated, and chemistry
and structure of the coating were studied by variety of
analytical tool. A Re-content as high as 77 at % or
Faradaic efficiency as high as 46%, were attained.
The formation of gold nanoelectrode [36] arrays
was investigated by electrodeposition of the metal
along the pores left on directionally solidified
NiAl-Re eutectics by selective dissolution of the
rhenium fibre. After the necessary pre-treatment for
the passivation of the NiAl matrix and dissolution of
the rhenium fibres to create arrays of nanopores
(diameter ~400 nm), the electrodeposition of gold into
the pores was initially investigated by examining the
growth of the deposits with the application of the
cathodic pulses.
According to the literature data [37], for obtaining
rhenium coatings the electrolytes containing fluoride
estimated to be more preferred compared with a
sulfate electrolytes. From these electrolytes rhenium
coatings on electrodes of copper, molybdenum, and
stainless steel may be deposited.
The authors [38] investigated the processes of
electrolytic production of rhenium coatings from the
electrolyte KCl-NaCl-ReCl4 with a current density
5-200 mA/cm2 at 680-970 °C. At this process the
dense coating of rhenium is forming, having thickness
20-40 microns and length up to 10 m. The diffusion
coefficient of Re4+ ion at 790 °C is 2.8 × 10-5, at
840 °C-3.5 × 10-5 cm2/sec.
The process of rhenium electrodeposition was
investigated by the method of measurements of
charging curves, measurements of overloading of
rhenium discharging and hydrogen on it, as well as by
defining a structure of sediment (by X-ray and
electron-microscopic methods). The authors [10, 11]
made a conclusion that in the process of
electrodeposition rhenium is saturating by hydrogen
(14-22 atomic%), main part of which is discharging at
room temperature and only 0.5 at % at > 500 °C. The
author [10] supposed a physical and chemical sorption
of hydrogen with formation of intrusion phases thru
ReH hydride. The electrodeposited metallic rhenium
has thin-dispersed structure and high tension (to 1,500
kg/cm2). There are known alloys of rhenium with
many elements, obtaining mainly by thermic method.
Alloys of rhenium with tungsten, molybdenum,
chrome, nickel and some others have a range of
valuable properties: high melting temperature, high
specific impedance, low volatility, heat fastness and
others. The valuable properties of rhenium alloys
allow applying them in most critical parts of various
equipment as well as for coating of electric contacts
and other parts, working in hard conditions [20, 21].
In connection with this the electrolytic production of
some rhenium alloys is a question of a great interest.
The works [20, 21, 41-76] were let in on the processes

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
189
of electrodeposition of rhenium together with other
metals on solid cathodes. Meyer A. [77] showed
probability of electrodeposition of alloys of rhenium
with a number of metals (Ni, Co, Fe, Zn, Cr, Pd, Rh,
Ag, Au) on platinum cathode. In such conditions a
discharging of hydrogen is lowering to 80%. The
sediments have good quality.
From one side, a rising of alloy may be explained
by rising of hydrogen discharge overstress at alloy
comparing with discharge it at rhenium [48]. From
other side resulting to alloy formation the enthalpy
(ΔH0) and free energy (ΔG0) change which obviously
have negative values.
A probability of joint electrodeposition of rhenium
and metals of ferric group were shown in works [1, 48,
49].
A special attention is to be paid to the works of L.M.
Netherton and M.L. Holt [76] in which was shown
probability of obtaining alloys Re-Ni and Re-Co with
various content of components depending of rhenium
concentration in electrolyte with high output by
current. They proposed two kinds of electrolytes
having following compositions: 225 g/L NiSo4·7H2O,
45 g/L NiCl2·6H2O, 1 g/L KReO4, 30 g/L H3BO3, to
second solution was added also citric acid in amount
of 70 g/L. From electrolyte with first composition (Ph
= 4.6) irrespective of current density an alloy was
deposited with high output by current (96-100%) and
with low content of rhenium. From second electrolyte
(Ph = 2.6), on the contrary, content of rhenium in
alloy achieved 60%, but output by current was ≤ 50%.
Alloy Re-Ni with 85-90% of rhenium also deposits
from electrolyte proposed in [21]. The electrolyte
contains 15 g/L KReO4, 5 g/L NiSO4, 50 g/L
(NH4)2SO4 and has pH = 2.5-3.0. At temperature
70 °C and current density 2-4 A/dm2 a coating
deposits with output by current ~90%. The alloy
Re-Ni in this electrolyte can be deposited only under
certain combination of pH and current density. In the
work [21] successfully was obtained the alloy Re-Ni
(85-90% of rhenium) with output by current 90% in
the electrolyte containing: KReO4-15 g/L;
NiSO4·7H2O-5 g/L; (NH4)2SO4-50 g/L, under pH =
2.5-3.0, current density 2-4 A/dm2 and temperature
70 °C with in dissolvable anodes. High output by
current connected with rise of overloading of
hydrogen due to co-deposition of nickel.
Were used ammonium-sulfate electrolytes having
various compositions [49, 68, 77]. Was defined
influence of current density, temperature,
concentration of rhenium and metal of ferrous group
to the process of electrodeposition two-component
alloys Re-Fe, Re-Ni, Re-Co. Was shown that a rise of
current density within the limits 2-20 A/dm (50 °C)
leads to rise of rhenium content in alloy. The
electrodeposition of alloys under optimal current
density (5 A/dm) promotes obtaining of shiny coatings
with output by current of alloy 100%. Particularities
of Re-Ni cathodic electrodeposition process were in
details highlighted in the works [48, 49]. The authors
highlighted that the mechanism of electrochemical
discharge of rhenium from perrhenate anion especially
with other metals is not clear, that impedes
development of optimal technological regimes. The
process of forming an alloy by the method of
polarization curves measurements was investigated,
chemical and phase composition of the alloy was
defined, output of alloy by current was calculated. The
authors came to the decision that nickel is discharging
with substantial depolarization in comparison with
separate discharging of metals. For rhenium discharge
also mitigates and the depolarization is 20-200 mV.
When investigating a possibility of obtaining of
triple alloy rhenium-nickel-chrome were used
electrolytes for obtaining of double alloys
rhenium-nickel, rhenium-chrome [11]. The obtaining
of triple alloy rhenium-nickel-chrome was proceeded
by group of Russian scientists [9].
During the investigation electrolytes for obtaining
defined double alloy were prepared and was added a
salt of appropriate third component. As a result of
series of experiments was defined that shiny coatings

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
190
of triple alloys are obtaining only in chrome-rhenium
bath in which was added nickel sulfate. The quality
alloys coatings containing: rhenium-0.5%;
nickel-0.28%; chrome-4.5% were obtained from the
bath of following composition (g/L): KReO4-50,
(NH4)2SO4-40, H2SO4-75, CrO3-15, NiSO4-45.
For electrodeposition of alloys Re-W the authors
Sominskaya Z.M. and others [9, 43] recommended
solutions on the base of perrhenate and tungsten with
addition of H2SO4 and (NH4)2SO4. As a complexion
agent which ties tungsten to soluble complex they
added citric acid. Alloy Re-W in a form of solid coating
or powder separates from solution containing potassium
perrhenate and ammonium (6-60 g/L of rhenium),
sodium tungstate (3-32 g/L of tungsten) ammonium
sulfate (50-200 g/L and citric acid (100 g/L). Maximal
output by current as in acidic so in alkaline conditions
is 10% and content of tungsten in alloy is 3%. The alloy
with maximal concentration of tungsten (10%) was
deposited with output by current ~1%.
Were also obtained alloys rhenium-copper with
various composition [9, 11]. A dense coating of
Re-Cu alloy containing 50% of copper is possible to
obtain in concentrated by rhenium electrolyte with
composition: 50 g/L KReO4 + 75 g/L H2SO4 + 40 g/L
(NH4)2SO4 + 1 g/L CuSO4. At the current density 100
A/dm2 and temperature 75 °C were obtained coatings
containing 36% copper. Alloys Re-Cu containing
2.4-3.0% of rhenium were extracted from electrolyte
with composition: CuSO4-125 g/L; H2SO4-45 g/L;
NaReO4 200 g/L at temperature75 °C and current
density 1-2 A/dm2.
To get the alloy Re with Cu authors [50] used
sulphate electrolyte. The gold and titanium electrodes
were used as cathode. Were studied rentgen graphic,
electron microscope and X-ray diffraction analyses
(ЕDХ, ХRD, SEM [50].
The authors of work [51] investigated the
mechanism of co-electrodeposition rhenium-nickel
alloy on copper backing from bath containing citric
acid.
For obtaining of coatings Re-Ir-Ni [52] a deposition
was carried out from various aquatic solutions on
copper backings with three electrodes by galvanostatic
method. The bath contained of iridium chloride,
ammonium perrhenate, nickel sulfamate and citric
acid.
The alloys of rhenium with nickel also had got the
authors of work [53]. For it was used three-electrode
cell, the polarization curves were measured in
galvanostatic conditions. The electrolyte had in
composition ammonium perrhenate, nickel sulphate
and citric acid. Was studied a mechanism for
nickel-rhenium alloys.
The authors of present work [54] were obtained
rhenium alloys with iron group (Me = Ni, Fe and Со).
The electrolyte had composition as follows:
ammonium perrhenate, nickel or cobalt sulfamate,
iron sulphate and citric acid and magnesium
sulfamate.
In their previous works authors reported about
co-electrodeposition of rhenium and metals of iron
group. In the present work [55] the authors in more
details investigated a mechanism of
co-electrodeposition.
Rhenium also was produced from secondary
materials containing rhenium and superalloy of nickel
clearly highlighted in work [56]. Were investigated at
constant potential electrolyse thin coatings CuIIRe at
electrolytic reduction CO2. The reduction products
were analyzed by FTIR and gas chromatography-mass
spectrometry. Were also studied out triple alloys on
indium-tin oxide coated by glass substrates from
acidic peroxo-polymolybdo-perrhenate solution.
Triple alloy Ni-Co-Re was investigated in alkaline
environment and their kinetic parameters were
determined. The authors [60] in this study gave data
on the production and use of rhenium and its alloys.
Rhenium-nickel alloy was also obtained by authors
[61]. Was investigated an influence of temperature,
current density, composition of electrolyte on alloy
composition. The electrolyte has the composition as

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
191
follows: ammonium perrhenate, nickel sulfate and
citric acid. For it was used electron microscopy (SEM),
X-ray diffraction (XRD) and X-ray fluorescence
(XRF).
A magnetic material based on
cobalt-nickel-rhenium-tungsten-phosphorus
(Co-Ni-Re-W-P) composition has been developed by
electrochemical deposition [62]. With proper control
of process conditions, hard magnetic films with high
out-of-plane remanent magnetization (Mr) of 3.11 kG
and coercivity (Hc) of 2.33 kOe are achieved.
Fabrication of Co-Ni-Re-W-P in the form of
microcylindrical arrays of ~50 µm diameter and 90
µm height enhances the vertical anisotropy to a
vertical Mr of 5.15 kG and Hc of 2.02 kOe. The
materials and fabrication technique of microstructures
as reported could be applied for the fabrication
technique of microstructures as reported could be
applied for the fabrication of magnetic
microelectromechanical systems. [62] The authors [63]
prepared from aqueous solutions with citric acid as
complex forming agent on a surface of Cu-substrate
coatings Ni-Re-P (Re = Ce, Nd). At 385 °C with the
amount of rhenium 30% (weight %) were obtained
amorphous coatings. Rhenium films with various
amount of copper were obtained. Qualitative deposits
Re-Cu (50%) were obtained from concentrated
solutions of rhenium: 50 g/L KReO4 + 75 g/L H2SO4
+ 40 g/L (NH4)2SO4 + 1 g/L CuSO4. At 75 °C, 100
A/dm2 were obtained films with 36% Cu. From the
solution CuSO4 -125 g/L, H2SO4-45 g/L, NaReO4-20
g/L at 1-2 A/dm2 were obtained films with
concentration of rhenium 2.4-3% Re.
For the obtaining rhenium-copper film was
proposed the electrolyte CuSO4 + NH4ReO4 [64]. At
the potentiostatic mode were obtained foils
rhenium-molybdenum and rhenium-tungsten coatings
[65]. The composition is 96% of H2SO4, potential-5-6
V, current density-60-70 mA/sm2.
The work [66] was dedicated to investigation of
some electro-physical properties of thin electrolytic
films of rhenium chalcogenides, as dynamic and static
voltammetric characteristics (VAC). Authors
investigated a typical VAC of diode structure
measured in static regime and found that diode
structure has polar-dependent switching effect. In
electrolytic layers of Pt-ReХe2-Al2O3 type, this effect
occurs right after supplying of voltage on diode
structure. The diode structure showed properties of
bi-stable switching. Were also investigated dynamical
characteristics of diode structure Me-Re-Хe2. The
investigation of VAC in dynamical regime has great
interest for interpretation of phenomena forming the
switching effects. Data obtained in present work
showed that the structure based at thin films of
rhenium chalcogenides, has VAC with S- and
N-shaped sectors of negative impedance (NI) both for
direct and reverse current direction. In contrast of
other devices with NI the elements basing on
mentioned alloy have simple production technology
and can work at wide range of temperatures. This
property let us suggest that devices basing on thin
films of rhenium chalcogenides may find wide using
in various devices in telemechanics, automation
computing technique.
At the conference which has been held in the
Moscow 2013 our work “The electrophysical
properties of thin films of rhenium chalcogenides
obtained by electrochemical method” was presented.
Our results found confirmation in the works by L.
Agapova and V. Guro [67-68].
3. Methods for obtaining alloys in system
Re-X (X = S, Se, Te)
The obtaining of chalcogenides can be performed
by various methods, defined by physics-chemical
particularities of synthesized compounds and initial
matters.
For obtaining of chalcogenides are used various
methods: (a) direct synthesis from elements by
alloying; (b) absorption from gaseous phase; (c)
obtaining of chalcogenides from salts solutions; (d)

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
192
electrochemical method [69-75]. Practically are using
all abovementioned methods. In the works [76-84]
widely were studied the system Re-X (X = S, Se, Te).
Rhenium forms with tellurium compounds having
various compositions of tellurides (Re-Te. In the
system Re-Te are known following tellurides: Re2Te,
ReTe, Re3Te2, ReTe2, Re2Te5, Re2Te7. A synthesis
and investigation of rhenium tellurides was begun
comparatively of late. A formation of rhenium
tellurides in binary system Re-Te is shown in [80]. A
diagram of conditions in this system was made basing
the data of thermic analysis, and there are three
compounds in system Re-Te: ReTe2, Re2Te5, Re2Te7.
Most tellurized compound in system is ditelluride
ReTe2 (42.15% mass. of rhenium), the melting
temperature of which is 965 °C. Crystal lattice of the
rhenium ditelluride is rhombic and the parameters of
the lattice are following: a = 12.987 ± 0.007 Å; b =
13.055 ± 0.008 Å; c = 14.271 ± 0.008 Å.
The system Re-Te was investigated also by authors
[78] and according the data of thermic and X-ray
phase analysis was drawn a diagram of a condition of
this system. In difference with of the work [80] here
an interaction of rhenium and tellurium was
investigated in whole interval of concentration.
The authors [80] pointed out bad reproducibility of
experiments results and supposed that ReTe2 exists
within the limits of ReTe2.04 to ReTe2.47. Rhenium
ditelluride is a dark gray powder, continually resistant
to air and soluble in hot sulfuric acid
S. Furusev and A. Krekzsus [84] prepared rhenium
ditelluride by heating of weighted stoichiometric
amounts of components in evacuated and sealed
quartz ampoule during twenty days at the temperature
700 °C. After dispersing the samples were annealed in
the interval of temperatures 500-1100 °C and then
cooled in icy water. The authors made a supposition
that crystal lattice of rhenium ditelluride is rhombic.
Rhenium tellurides were also obtained by action of
Te and H2Te vapors in hydrogen flow to powdered Re
and ammonium perrhenate using technologies [6, 80].
As a result were obtained dark grey powders with
increased content of tellurium. Very bad
reproducibility of experiments is to be mentioned.
Samples containing 68.35% of Te are two-phased and
consist of ReTe2+Te. Despite of all efforts the authors
could not get samples exactly corresponding to ReTe2.
Thus, rhenium telluride are unstable even at
comparatively low temperatures, together with excess
of hydrogen, being deoxidant, causes bad
reproducibility of experiments as well as unsuccessful
efforts to obtain a compound with the composition
ReTe2. Abovementioned shows that using these
methods only solid samples or powders of rhenium
telluride can be obtained. Was investigated a structure
of crystals of Re2Te5 grown by gas transporting
reaction. The parameters of rhombic lattice Re2Te5
were close to ones found in [84] for the compound
ReTe2 what is an additional confirmation of possible
wide range of homogeneity between compounds
ReTe2 and Re2Te5, presence of which was shown in
[78, 80].
Thus, rhenium creates with tellurium a range of
compounds appropriating to different stages of
oxidation and most of these compounds can be
obtained by direct interaction of rhenium and
tellurium. For rhenium selenides are known following
compounds: Re2Se7 (heptaselenide), ReSe2
(diselenide), ReSe (monoselenide), Re3Se2 and Re2Se5.
Re2Se5 (rhenium pentaselenide) was obtained by
running H2Se through solution of KReO4 with
addition of potash for linking of some amount of
selenium discharging during the reaction. Rhenium
diselenide ReSe2 first was obtained by heating of
Re2Se in vacuum at 330 °C during 9 hours according
to reaction:
Re2Se7 → 2 ReSe2 + 3 Se.
Obolonchik Ch.A. and Mikhlina T.M. proposed a
method of obtaining rhenium diselenide by action of
dry H2Se to metallic rhenium or ammonium
perrhenate [79]. The optimal temperature of synthesis
in both cases is 700 °C.

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
193
Re + H2Se = ReSe2 + 2 H2.
2 NH4ReO4 + 7 H2Se = 2 ReSe2 + 2 NH3 + 8 H2O + 3
Se.
Rhenium diselenide is stable in hydrogen flow at
heating to 400 °C then, if the temperature continues to
rise, selenium detaches and at the temperature 900 °C
and more rhenium diselenide fully looses selenium
and stays pure metallic rhenium.
The formation of rhenium selenide ReSe2 is well
confirming by roentgenographic examination of
reaction products. In the work [85] was made
roentgenographic examination of part of system Re-Se
in an interval of concentrations 50-70% at. Se. To this
aim were synthesized and examined samples having
following composition: ReSe (50% at. Se), ReSe2
(66.6% at. Se), Re2Se5 (71.43% at. Se) and ReSe3
(75% at. Se). X-ray analysis of obtained samples
showed that in examined range of system exists only
one phase-ReSe2. ReSe and Re3Se2 are dark grey
roentgenoamorpfous powders. They do not dissolve in
water and organic solvents.
ReSe2 is a powder of black color, without smell
with density (according to pycnometric test) being
equaled 8.27 g/cm3. ReSe2 is entirely stable on air,
fully soluble while heated in hydrogen peroxide and in
mixed of nitric and sulfuric acids. In concentrated HCl
ReSe2 does not dissolve as in cold so when heated. In
nitric, sulfuric acids and in aqua regia it is partially
soluble when heated. The solution in mixed HNO3 and
H2O2 begins at cold and entirely runs under heating.
In 25% ammonia and ethyl alcohol rhenium diselenide
does not dissolve. ReSe2 is active catalyst for n-butane
dehydration to divinyl (the temperature of the reaction
~650 °C).
At present there are known several methods of
rhenium sulfides production. In system Re-S was
defined existence of rhenium sulfides with
composition: ReS, Re2S3, ReS2, Re2S5, ReS3 and
Re2S7 [41, 85]. Only ReS2 of all rhenium sulfides can
de produced by direct synthesis of components, other
compounds are to be produced by indirect methods.
Most stable compound of rhenium with sulfur is
ReS2. In the works rhenium disulfide was obtained by
direct interaction of elements in evacuated ampoules,
and in the study of C. Odent [82] by dissociation of
higher sulfides. It can be obtained by sulfidizing of
metallic rhenium [82] rhenium oxides (ReO2). ReS2 is
black powder, stable on air, has a density 7.506 g/cm3,
it does not dissolve in H2SO4, in HCl, as well in alkali.
The authors [49] supposed hexagonal one, MoS2 type.
Re2S5 (rhenium pentasulfide) is obtaining by long
pumping of hydrogen sulfide through acidic (1-4 HCl)
solution of perrenate [3] or in heated mixture of
rhenium perrhenate and sodium thiosulfate solutions.
As seems from abovementioned, using these
methods is possible to get rhenium chalcogenides in a
form of massive samples or powder [83, 84]. As
presently wide use in technique find rhenium
chalcogenides in a form of thin films there are needed
additional operations for conversion of
abovementioned samples to obtain thin films. In
connection with this an electrochemical method of
production thin films of rhenium chalcogenides on
conducting base takes on a distinctive importance.
The authors Sharipova N.S. and Songina O.A. [47]
investigated electrochemical behavior of selenium (VI)
with presence of rhenium (VII) at mercury dripping
electrode. Was defined that rhenium (VII) in this
condition shows one well defined wave in the range of
potentials -0.35-0.8 *n.k.e. At joint presence of
rhenium and selenium appears maximum at potential
-0.7 V, no observed before separately for rhenium or
for selenium, which carries catalytic character and
which can be used as calibrate graph for quantitative
definition of selenium.
We also have been studied semi-conducting
coatings of chalcogenides rhenium from different
electrolytes [66, 69-75, 81-83, 85-99].
For obtaining semi-conducting of Re-Se alloy we
investigated joint electrodepositing of rhenium and
selenium from alkaline [75] and sulfate [69, 70, 99]
electrolytes. To obtain Re-Se alloy from sulfate

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
194
electrolyte [69, 99] was used the electrolyte with
following composition (mole/L): 0.1-0.01 SeO2 +
0.01-0.1 NH4ReO4 + 2.0 H2SO4, a current density 10
mA/cm2, temperature 75 °C. For first time were
defined main regularities of co-deposition of rhenium,
selenium and rhenium by selenium from sulfate
electrolyte. Was found, that under definite conditions
of electrolyte the joint electrodeposition of rhenium
and selenium takes place. At first time was carried out
physics-chemical investigation of alloy forming in
system Re-Se when joint electrodeposing rhenium and
selenium from sulfate electrolyte. Basing on the
experimental data was proposed the interpretation of
cathodic process carrying out at various meanings of
cathodic potential. Basing on experimental data was
developed optimal composition of electrolyte and
electrolysis regime for obtaining quality
semi-conducting coatings of rhenium chalcogenides
from sulfate electrolyte [99]. For obtaining Re-Se
alloy from alkaline electrolyte we used the electrolyte
following composition (mole/L): 0.01-0.1 M
NH4ReO4 + 0.01-0.1 M SeO2 + 1-3 NaOH alkaline
electrolytes.
At first time using potentiostatic,
temperature-kinetics and voltammetric methods were
investigated kinetics and mechanism of separate and
joint electrodeposition of rhenium with chalcogenes
from alkaline electrolyte [75]. It was defined that the
mechanism of joint electrodeposition of rhenium with
selenium from alkaline electrolyte depends of
concentration of bivalent selenium obtained on
cathode, which optimizes reduction of rhenium with
forming of chemical compounds ReSe2. At a cathode
current density of 4 mA/cm2, using an electrolyte of
composition 0.05 M NH4ReO4 +0.05 M SeO2 + 1 M
NaOH, we obtained lustrous ReSe2 (54 wt% Re)
coatings. The formation of ReSe2 was confirmed by
XRD. At first time were investigated some
physics-chemical properties of thin coatings of Re-Se
alloys.Re-Te alloy we proposed and chloride-sulfate
[91, 97] electrolytes. For obtaining semi-conducting
alloy Re-Te in a form of thin films was found optimal
regime and electrolyte. For obtaining thin films of
rhenium chalcogenides in the work was proposed the
electrolyte and optimal regime for producing alloys.
To obtain thin films ReTe2 (rhenium ditelluride) is
necessary to carry out electrolyses at current density 2
mА/сm2, temperature 75 °C from electrolyte .
It was proposed an electrolyte and optimal regime
to get rhenium-tellurium thin films in chloride-borate
electrolyte [93, 94, 96] for obtaining alloys Re-Te.
Using potentiostatic, temperature-kinetic,
voltammetric methods were investigated kinetics and
mechanism of separate and co-electrodeposition of
rhenium and tellurium from chloride-borate
electrolyte. Was defined that a discharge of tellurium
complex on cathode runs through occurring of
intervening particles, arriving as a result of preceding
chemical reaction of tellurium complex dissociation.
At co-deposition of rhenium and tellurium from
chloride-borate electrolyte a main role plays a
chemical activity of tellurium connected with its
disposal to deep deoxidation and formation of Te2- at
the surface of a cathode. It changes a nature of
tellurium electrode and leads to co-electrodeposition
of rhenium and tellurium with formation of chemical
compound ReTe. It was found that finely crystalline,
glittering coatings with a composition of ReTe2 (42
wt% Re) and a thickness of up to 5 цш formed from
the electrolyte containing (M) 0.05 NH4ReO4 + 0.003
TeO2 + 3 HCl + 0.05 H3BO3 (electrolysis time 30 min,
current density 1.2 A/dm2, 0.25-0.20 V, s.c.e.).
According to X-ray phase analysis data, ReTe2
crystallized as an orthorhombic compound with unit
cell parameters a = 1.301 nm, b = 1.307 nm, and с =
1.428 nm [94].
Alloys of rhenium and sulfur are using as a
photosensitive material in semi-conducting technique
in a form of coatings. In works [72, 93-94] was widely
investigated co-electrodeposition of rhenium and
sulfur from sulfate and thiosulfate electrolyte [87].
Using the method of voltammetry was investigated a

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
195
process of electrodeposition of rhenium sulfide films
at platinum and titanium cathodes. Was proposed the
mechanism of this process including
electro-deoxidation of Re(VII) to Re(0) and chemical
interaction of Re with S. Was defined that to quality
and composition of films substantially influences a
concentration of main components in electrolyte, a
temperature, current density and acidity of electrolyte.
Using X-ray testing was proved that in
co-electrodeposition of Re and S at cathode is forming
chemical compound of rhenium disulfide ReS2. It was
defined that obtained coatings have p-tip conductivity.
The electrodeposition of thin films Re-S from aqueous
solutions containing ammonium perrhenate,
thiocarbamide and sulfuric acid was made in the work
[72]. The electrolytic alloys Re-S were obtained from
the electrolyte of the following composition: 0.1 ×
103-2.0 ×103-MNH4ReO4; 1 × 10-3-3 × 10-3
M(NH2)2CS; 0.5 × 10-3-1.23 × 10-3 MH2SO4; pH =
1-1.5, current density being 25-45 mA/sm2.
At first time was physical-chemical investigation of
alloy formation in Re-S system and was defined that
co-electrodeposition of rhenium and sulfur depends of
adsorption of colloidal sulfur on cathode, and as
rhenium so sulfur deposit by depolarization which
affirms the formation of chemical compound ReS2.
The rhenium alloys have found wide application in
radio technique, electronics, semi-conducting industry
and other fields of modern technique. In this
connection undoubted practical and theoretical interest
has the electrochemical deposition of rhenium.
Also in the review indicates that the rhenium alloys
are widely used in electronics, electrical engineering,
electronics and semiconductor industry and other
areas of modern technology. Thus, from
abovementioned review is clear that acidic and
alkaline solutions are good electrolytes for the
production of coatings of rhenium alloys.
Therefore, a detailed study of the process of
co-electrodeposition of rhenium with chalcogenides
of alkaline and acidic electrolytes has practical and
theoretical interest.
References
[1] The Proceeding of 4th All-union Conference on Problems
of Rhenium. Coll. “Rhenium: Chemistry, technology,
analysis”, Publishing House “Nauka”, Moscow, 1976, p.
203. (in Russian)
[2] V. Borisova, A.N. Yermakov, The Analytical Chemistry
of Rhenium, Publishing House “Nauka”, Moscow, 1974,
pp. 319-320. (in Russian)
[3] The Proceeding on the Occasion of 50 years of Discovery
of Rhenium. Coll. “The Investigation and Application of
Rhenium Alloys”, Publishing House “Nauka”, Moscow,
1975, p. 203. (in Russian)
[4] D.G. Kochergina, The Production and application of
rhenium in capitalist countries, Nonferrous Metals. 8
(1957) 63-66. (in Russian)
[5] I. Drutse. “Rhenium”, Il., Moscow, 1951, p. 62. (in
Russian)
[6] Coll. “Rhenium in Modern Technique”, Publishing
House “Nauka”, Moscow, 1970, p. 201. (in Russian)
[7] Coll. “Rhenium”, Publishing House of Academy of
Sciences of USSR, Moscow, 1961, p. 124. (in Russian)
[8] Coll. “Rhenium”, Publishing House of Academy of
Sciences of USSR, Moscow, 1964, p. 259. (in Russian)
[9] Y.F. Speranskaya, In coll. Electrochemistry of Rhenium,
Publishing House “Gylym”, Alma-Ata, 1990, p. 253. (in
Russian)
[10] O.A. Suvorova, The electro-deposition of rhenium in
water solutions, D.Sc. dissertation, Moscow, 1962, p. 280.
(in Russian)
[11] O.A. Suvorova, Rhenium, in: The Proceeding of 4th
All-union Conference on Problems of Rhenium, Moscow,
1961, p. 163. (in Russian)
[12] V.N. Varypayev, V.L. Krasikov, The electrochemical
behaviour of rhenium-graphite electrode, Applied
Chemistry Journal 53 (3) (1980) 586. (in Russian)
[13] S.N. Vinogradov, The Electroplating by
Palladium-Rhenium Alloys, Publishing House
“Radiopromyshlennost” (Radio Industry), 1992, pp.
24-25. (in Russian)
[14] M. Bouroushian, Electrochemistry of Metal
Chalcogenides, 2010, XII, p. 358.
[15] Shao Minhua, Electrocatalysise in fuel Cells, 2013, XVI,
p. 745.
[16] A.Y. Gavrilenko, A.L. Rotinyan, V.N. Varypayev,
Regularities of Hydrogen Discharge on Electrochemical
Rhenium in Sulfate Solutions, Electrochemistry Moscow
15 (10) (1979) 1519-1523. (in Russian)
[17] I.I. Gvozdyova, A.I. Zhurin, Electrochemical properties
of rhenium, The Works of Leningrad Polytechnic

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
196
Institute 188 (1957) 212-224. (in Russian)
[18] A.A. Nikitina, V.A. Solovyova, Z.M. Sominskaya, et al.,
About mechanism of rhenium electrodeposition,
Electrochemistry Moscow 1 (1965) 748-751. (in Russian)
[19] A.A. Nikitina, Z.M. Sominskaya, A.T. Vagramyan,
Concerning mechanism of rhenium electrodeposition,
Applied Chemistry Journal 39 (10) (1966) 2248-2251. (in
Russian)
[20] E.A. Salakhova, V.A. Mejidzade, The electrodeposition
of rhenium from sulfate electrolyte, Journal of Chemical
Problems Baku 3 (2006) 588-580. (in Russian)
[21] N.V. Korovin, M.A. Ronzhin, The electrodeposition of
rhenium from sulfate-ammonium solutions, Journal of
Physical Chemistr 35 (1965) 660-663. (in Russian)
[22] V.L. Krasikov, Concerning the mechanism of rhenium
electrodeposition, Electrochemistry Moscow 1 (10) (1981)
1518-1521. (in Russian)
[23] O.A. Suvorova, M.V. Ippolitova, Concerning discharge
of rhenium by electrolyse, Publishing House of Academy
of Sciences of Kazakhstan SSR 88 (4) (1951) 81-103. (in
Russian)
[24] A.V. Uscategui, E. Mosquera, et al., Transmission
electron microscopy study of electrodeposited rhenium
and rhenium oxides, Materials Letters (2013) 44-46.
[25] R. Deschenaux, T. Ruch, et al., Synthesis,
characterization, and electrochemical and photophysical
properties of rhenium (I) and ruthenium (II) complexes of
2,2- bipyridine ligand functionalized ß-cyclodextrins,
Helvetica Chimica Acta 78 (3) (1995) 619-628.
[26] G, Valenti, E.J. Orelly, et al., Cover picture:
Electrochemically induced release of a luminescent probe
from a rhenium containing metallopolymer, Chem. Plus.
Chem. 78 (1) (2013) 2.
[27] A.A. Pallant, Monograph metallurgy of rhenium, Nauka,
2007, p. 298.
[28] J.O. Zerbino, A.M.C. Luna, et al., A comparative study of
electrochemical and optical properties of rhenium
deposited on gold and platinum, Journal of the Brazilian
Chemical Society San Paolo 13 (4) (2002).
http://dx.doi.org/10.1590/S0103-50532002000400016.
[29] U.O. Hafeli, M.C. Warburton, U. Landau,
Electrodeposition of radioactive rhenium onto stents to
prevent restenosis, Biomaterials. 19 (10) (1998) 925-933.
[30] A.M. Affoune, A. Saila, et al., Electrochemical behaviour
of silver and rhenium electrodes in molten alkali fluorides,
Journal of Applied Electrochemistry 37 (2007) 155-160.
[31] M.A. Yakovlev, The study, modeling and optimization of
the processes of extraction of rhenium from
multi-componentalloys, Ph.D. thesis, 2005, Vladikavkaz,
Russia. (in Russian).
[32] L.G. Holz, The voltammetric determination of rhenium in
raw and anthropogenic materials, Ph.D. thesis, Tomsk,
Russia, 2006, p. 121. (in Russian)
[33] S. Szabo, I. Bakos, Electrodeposition of rhenium species
onto a gold surface in sulfuric acid media, Journal of
Solid State Electrochemistry 8 (3) (2004) 190-194.
[34] R. Schrebler, P. Cury, et al., Study of the
electrodeposition of rhenium thin films by
electrochemical quartz microbalance and X-ray
photoelectron spectroscopy, Thin Solid Films 483 (1-2)
(2005) 50-59.
[35] A. Naor-Pomerantz, N. Eliaz, Elektrodeposition of
rhenium-tin nanowires, Elektrochimica Acta 56 (18)
(2011) 6361-6370.
[36] B.B. Rodriguez, A.W. Hassel, Electrochemical nucleation
and growth of gold on embedded rhenium nanowires, J.
El. Chem. and Plat. Tech. 41 (10) (2008)47-55
[37] N.D. Ivanova, S.V. Ivanova, E.J. Boldyren,
Electrodeposition of rhenium coatings, Funct. Mater. 7 (2)
(2000) 350-352.
[38] H.C. Sum, W.H. Ling, Fabrication of photovoltaic cell
from rhenium containing polymer, in: 4th Conference on
Organic Photovoltaics, San Diego, CA, 2003, pp.
254-261.
[39] E.A. Salakhova, V.A. Medjidzade, et al., The
electrodeposition of rhenium in alkaline and acidic
electrolytes, Journal of Chemistry and Chemical
Engineering 6 (5) (2012) 489-494.
[40] E.A. Salakhova, V.A. Medjidzade, et al., The electrolytic
subsidence of rhenium from acidic electrolytes, in:
Seventh International Symposium on Technetium and
Rhenium-Science and Utilization, Moscow, Russia, 2011,
p. 112. (in Russian)
[41] A.I. Zelikman, M.V. Teslitskaya, Obtaining of rhenium
bisulfide from the perrhenat kalium, Journal of Inorganic
Materials 7 (4) (1971) 314-315.
[42] N.V. Korovin, M.A. Ronzhin, The electrodeposition of
rhenium-nickel alloy on cathode, Journal of Physical
Chemistry 33 (1960) 374-377. (in Russian)
[43] A.A. Nikitina, Z.M. Sominskaya, A.T. Vagramyan,
Electrodeposition of rhenium-tungsten alloy,
Electrochemistry Moscow) (1968) 82-86. (in Russian)
[44] V.A. Tereshkin, P.M. Vyacheslavov, V.N. Varypayev,
Electrodeposition of rhenium-tungsten alloy, Applied
Chemistry Journal 6 (1976) 1394-1396. (in Russian)
[45] V.F. Travkin, Exstraction-electrolytical technology of
production of rhenium from solutions having multiple
salty composition, Nonferrous Metallurgy Moscow 4
(1998) 32-36. (in Russian)
[46] V.A. Tereshkin, Electrolytical deposition of
rhenium-tungsten alloy, Ph.D. dissertation, LTI named
Lensoviet, 1976, p. 140.
[47] N.S. Sharipova, O.A. Songina, Concerning catalytic
reduction of rhenium (VI) on mercury pumping electrode,

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
197
in: The Abstract of Report on III all-union Conference on
Chemistry and Technology of Chalcogenes and
Chalcogenides, Karaganda, 1986, p. 295.
[48] A.M. Pishikin, M.Ya. Popeka, The electrodeposition of
sparkling electroplates of rhenium and rhenium-nickel
alloys, Sparkling and Combinated Metallic Coatings,
1967, p. 3. (in Russian)
[49] A.M. Pishikin, M.Ya. Popeka, Alloy electrodeposition
nickel-rhenium, Journal of Applied Chemistry 44 (5)
(1971) 1015. (in Russian)
[50] R. Schrebler, M. Merino, P. Cury, et al.,
Electrodeposition of Cu-Re alloy thin films, Thin Solid
Films 388 (1-2) (2001) 201-207.
[51] F. Contu, S.R. Taylor, Further insight into the mechanism
of Re-Ni electrodeposition from concentrated aqueous
citrate baths, Electrochimica. Acta. 70 (2012) 34-41.
[52] M.C. Sagiv, N. Eliaz, et al., Incorporation of iridium into
electrodeposited rhenium-nickel alloys, Electrochimica.
Acta. 88 (2013) 240-250.
[53] A. Naor, N. Eliaz, et al., Electrodeposition of
rhenium-nickel alloys from aqueous solutions,
Electrochimica. Acta. (2009) 6028-6035.
[54] A. Naor, N. Eliaz, et al., Electeodeposition of alloys of
rhenium with iron-group metals from aqueous solutions, J.
Electrochem. Soc. 157 (7) (2010) D422-D427.
[55] A. Naor, N. Eliaz, et al., Direct experimental support for
the catalytic effect of iron-group metals on
electrodeposition of rhenium, Electrochemical and
Solid-State Letters 13 (12) (2010) D91-D93.
[56] A.A. Palant, O.M. Levchuk, et al., Complex
electrochemical processing of the metallic wastes from a
rhenium-containing nickel superalloy in sulfuric acid
electrolytes, Russian Metallurgy 2011 (6) 589-593 (in
Russian).
[57] R. Schrebler, P. Cury, et al., Study of the electrochemical
reduction of CO2 on a polypyrrole electrode modified by
rhenium and copper-rhenium microalloy in methanol
media, Journal of Electroanalytical Chemistry 533 (1-2)
(2002) 167-175.
[58] B.P. Hahn, K.J. Stevenson, Electrochemical synthesis and
characterization of mixed molybdenium-rhenium oxides,
Electrochimica. Acta. 55 (22) (2010) 6917-6925.
[59] V. Pashova, L. Mirkova, et al., Electrocatalytic materials
of NiCoRe electrodeposited alloy for alkaline water
electrolysis, ECS Transactions 25 (35) (2010) 395-401.
[60] A. Naor, N. Eliaz, Properties and applications of rhenium
and its alloys, AMMTIAC 5 (1) (2010) 11-15
[61] P. Zabinski, A. Franczak, et al., Electrodeposition of
functional ni-re alloys for hydrogen evolution, ECS
Transactions 41 (33) (2012) 39-48.
[62] A. Takada., K. Okada, Electrodeposited Co-Ni-Re-W-P
thick array of high vertical magnetic anisotropy,
Magnetics, IEEE Transactions 41 (10) (2005) 41.
[63] W. Lingling, T. Liming, H. Greifang, Preparation of
amorphous rare-earth films of Ni-Re-P (Re-Ce, Nd) by
electrode position from an aqueous bath, Surface and
Coal. Technol. 192 (2-3) (2005) 208-212.
[64] V. Povetkin, S. Skifsky, E. Koreshkov, Electrolyte for
deposition of alloy copper-rhenium Patent 224560, MPK
25L3/38, Tyumen, Russia, 2004. (in Russian)
[65] N. Mazurenko, S. Garmonov, K. Nagulin,
Electropollarization molibde-rhenium and
wolfram-rhenium alloys in the liquid, coll. Electroenergy,
Kazan, 1998, pp. 104-107. (in Russian)
[66] E.А. Salakhova, V.А. Мajidzade, et al., The
electrodeposition properties of thin films of Rhenium
Chalcogenides obtained by electrochemical method, in:
Conference “Rhenium. Scientific Investigations,
Technological Development, Industrial Application”,
2013, p. 114. (in Russian)
[67] L. Agapova, et al., Electrolytical deposition Re-contained
alloys from aquatique liquids, Renium. Scientefic
Investigations, Technological Development, Industrial
Application, 2013, p. 90. (in Russian)
[68] V. Guro, Reducing waste of Re-contained alloys with
obtaining pure ammonium perrenhate, in: Conference of
Renium. Scientific Investigations, Technological
Development, Industrial Application, 2013, p. 82. (in
Russian)
[69] E.A. Salakhova, Main regularities of electrodeposition of
rhenium with selenium from sulfate electrolyte,
Azerbaijan Chemical Journal Baku 4 (2003) 140-144. (in
Russian)
[70] E.A. Salakhova, The investigation of some
electrophysical properties of thin films of
rgenium-selenium alloys, Azerbaijan Chemical Journal 2
(2001) 74-78. (in Russian)
[71] E.A. Salakhova, Co-electrodeposition of rhenium (VIII)
with tellurium (IV) from chloride-sulfate electrolyte,
Azerbaijan Technical University “Kimya, Biologiya,
Tibb” 1 (2002) 4-9. (in Russian)
[72] E.A. Salakhova, Co-deposition of rhenium and sulfur
from thiocarbamide electrolyte, Azerbaijan Chemical
Journal 3 (2003) 73-77. (in Russian)
[73] E.A. Salakhova, Electrophysical properties of ReSe2 and
Re2Se7 thin films, Azerbaijan Chemical Journal 1 (2002)
77-81. (in Russian)
[74] E.A. Salakhova, The electrochemical production of thin
films of rhenium ditelluride, Azerbaijan Chemical Journal
2 (2005) 123-126. (in Russian)
[75] E.A. Salakhova, The electrochemical production of thin
films of system rhenium-selenium alloys, Inorganic
Materials Journal 39 (2) (2003) 142-146.
[76] L.E. Netherton, M.L. Holt, Electrodeposition of Rhenium

The Electrochemical Deposition of Rhenium Chalcogenides from Different Electrolytes
198
from aquatic solutions, J. Electrochem. Soc. 95 (6) (1999)
324.
[77] A. Meyer, Studying for electrodeposition rhenium,
Oberfläche-Surface 11 (4) (1970) 117. (in French)
[78] T.Ch. Kurbanov, R.A. Dolyatschina, Re-Te system,
Journal of Inorganic Materials 22 (4) (1977) 1137-1138.
(in Russian)
[79] Ch.A. Obolonchic, T.M. Michlina, Obtaining and
properties of rhenium selenides, Ukraine Chemistry
Journal 30 (1964) 1037-1040. (in Russian)
[80] A.A. Opalovsky, F.E. Fedorov, New selenides and
rhenium-tellurides publishing, Journal of Inorganic
Materials 1 (2) (1971) 144-148. (in Russian)
[81] S. Furuseth, A. Kjekshus, The Systems Rhenium-Arsenic,
Rhenium-Antimony, Rhenium-Bismuth,
Rhenium-Tellurium, and Niobium-Antimony-Tellurium,
Acta chem. Scand 20 (1) (1966) 245-250
[82] C. Odent, Contribution to the study of sulfide and l hemi
pepta sulfide, Re. Rew. Chem. Miner. 6 (5) (1969)
933-935 (in French)
[83] A. Nemudry, R. Scholhorn, Re6S12, a new binary rhenium
cluster chalcogenide, J. Chem. Soc. Chem Comm. (1994)
2617-2618.
[84] C. Fischer, et al., Structure and photoelectrochemical
properties of semiconducting rhenium cluster
chalcogenides: Re6X8Br2 (X = S, Se), J. of Alloys and
Compounds 178 (1-2) (1992) 305-314.
[85] N.W. Alcock, A. Kjekshus, The crystalline structure of
ReSe2, Acta Chem. Scand 19 (1) (1965) 79-94.
[86] E.A. Salakhova, V.A. Majidzada, Semiconducting
properties of thin covers of rhenium chalcogenides, J.
Chemistry and Chemical Technology 52 (5) (2009) 117.
(in Russian)
[87] S.V. Mamedova, M.N. Mamedov, E.A. Salakhova, The
Electrochemical Deposition of Re-S Alloy on Pt
substracte 1st Electrochemistry, Days Istanbul, 1999,
40-42
[88] E.A. Salakhova, F.S. Novruzova, The Electrochemical
Properties of Thin Alloys Rhenium-Selenium, XIV
Ulusal Kimya Kоnqrеsi, Diyarbakir, 2001, 164.
[89] E.A. Salakhova, Kinetics and Mechanism of Rhenium
Discharge in Alkaline Electrolyte, XVI Ulusal Kimya
Konqresi, Turkiye, 2002, p. 535.
[90] E.A. Salakhova, The electrodeposition of the alloys of the
rhenium sulphide, in: 5th International Conference, Solid
Stat Chemistry, Bratislava, 2002, p. 54.
[91] E.A. Salakhova, The Electrodeposition of the
semi-conductor alloys of the renium chalcogenides from
the sulfate electrolyte, in: 51st LSE Meeting, Warsaw,
2000, p. 45.
[92] B. Schubert, H. Tributsch, Electrochemically formed
transient ReS2/Re2O7 heterojunetion with high energy
conversion efficiency, Journal applied Electro Chemistry
20 (1990) 786-792.
[93] E.A. Salakhova, V.A. Majidzada, The electrodeposition
of rhenium-tellurium alloy in chloride-borate electrolyte,
Chemistry and Chemical Technology 51 (2) (2008)
51-54.
[94] E.A. Salakhova, V.A. Majidzada, Electrochemical
preparation of thin rhenium-tellurium coatings
chloride-borate electrolyte, Russian Journal of
Electrochemistry 47 (8) (2011) 877-882. (in Russian)
[95] L. Bob, K. Wheler, Photoelectrochemistry of p-ReS2 and
p-ReSe2 in aqueoous solutions, J. Electrochem. Soc. 133
(2) (1986) 358-361.
[96] E.A. Salakhova, V.A. Mejidzadeh, K.F. Seyidova, P.E.
Kalantarova, Cathodic polarization under
co-electrodeposition of rhenium-tellurium alloy, Journal
Chemistry and Chemical Technology Ivanovo 51 (5)
(2008) 31-33. (in Russian)
[97] E.A. Salakhova, The obtaining of thin coatings of Re-Te
alloys from chloride-sulfate electrolyte and the influence
of different factors to the composition of alloy, Journal
Chemical Industry Today 6 (2008) 43-47. (in Russian)
[98] D.K. Kunev, The production of rhenium disulfide,
publishing house of academy of sciences of USSR,
Inorganic Materials 14 (2) (1978) 232-236.
[99] E.A. Salakhova, A.M. Aliyev, Obtaining the thin
semiconductive covering Re-Se from sulphate electrolyte,
Journal of Advanced in Materials and Physics Chemistry
2 (4) (2012) 253-255.