Preparation of highly dispersed Ni1-xPdx alloys for the decomposition of chlorinated hydrocarbons

Article abstract of DOI:10.1016/j.jallcom.2018.12.207

A convenient procedure to synthesize highly dispersed Ni_1-xPd_x alloys has been developed. The procedure is based on thermal decomposition in the reducing atmosphere of specially synthesized multicomponent precursor. The formation of single-phase solid solutions in the entire range of palladium concentrations was confirmed by powder XRD. The alloys have a porous structure composed of grains whose size depends on the synthesis temperature. The study of the catalytic properties of Ni_1-xPd_x alloys (5 wt% Pd) showed their high activity in the 1,2-dichloroethane decomposition process. After 5 h of catalytic experiment the yield of carbon material was 160 g_С/g_cat for Ni_1-хPd_х. This is more than 3 times higher than the yield of reference samples (porous Ni, Ni–Co, Ni–Cu). The carbon material formed has a segmented fibrous structure. It is characterized by high morphological uniformity. The specific surface area of the obtained carbon material is 580 m²/g.

Full text of DOI:10.1016/j.jallcom.2018.12.207

Accepted Manuscript
Preparation of highly dispersed Ni Pd alloys for the decomposition of chlorinated
1-x
x
hydrocarbons
Yuliya V. Rudneva, Yury V. Shubin, Pavel P. Plyusnin, Yury I. Bauman, Ilya V.
Mishakov, Sergey V. Korenev, Aleksey A. Vedyagin
PII:
S0925-8388(18)34763-7
DOI:
https://doi.org/10.1016/j.jallcom.2018.12.207
JALCOM 48848
Reference:
To appear in: Journal of Alloys and Compounds
Received Date: 9 November 2018
Revised Date: 13 December 2018
Accepted Date: 16 December 2018
Please cite this article as: Y.V. Rudneva, Y.V. Shubin, P.P. Plyusnin, Y.I. Bauman, I.V. Mishakov,
S.V. Korenev, A.A. Vedyagin, Preparation of highly dispersed Ni Pd alloys for the decomposition
1-x
x
of chlorinated hydrocarbons, Journal of Alloys and Compounds (2019), doi: https://doi.org/10.1016/
j.jallcom.2018.12.207.
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ACCEPTED MANUSCRIPT
Preparation of highly dispersed Ni1-xPdx alloys for the decomposition of chlorinated
hydrocarbons
Yuliya V. Rudneva a,*, Yury V. Shubin a,b, Pavel P. Plyusnin a,b, Yury I. Bauman c, Ilya
V. Mishakov b,c, Sergey V. Korenev a,b and Aleksey A. Vedyagin c
a
b
c
Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia;
Novosibirsk State University, Novosibirsk, Russia
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia;
*
Corresponding author. Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk,
Russia. E-mail address: rudneva@niic.nsc.ru (Yu.V. Rudneva)
Abstract: A convenient procedure to synthesize highly dispersed Ni1-xPdx alloys has been
developed. The procedure is based on thermal decomposition in the reducing atmosphere of
specially synthesized multicomponent precursor. The formation of single-phase solid solutions in
the entire range of palladium concentrations was confirmed by powder XRD. The alloys have a
porous structure composed of grains whose size depends on the synthesis temperature. The study
of the catalytic properties of Ni1-xPdx alloys (5 wt.% Pd) showed their high activity in the 1,2-
dichloroethane decomposition process. After 5 h of catalytic experiment the yield of carbon
material was 160 gС/gcat for Ni1-хPdх. This is more than 3 times higher than the yield of reference
samples (porous Ni, Ni–Co, Ni–Cu). The carbon material formed has a segmented fibrous
structure. It is characterized by high morphological uniformity. The specific surface area of the
obtained carbon material is 580 m2/g.
Keywords: Ni-Pd alloys; dispersed alloy; combined precipitation; 1,2-dichloroethane; alloy
catalysts; carbon fibers
1. Introduction
Over the past decades, the problem of reducing environmental pollution by highly toxic Cl-
containing organic wastes is of great interest. These wastes are accumulated as a result of the
growing production of polymer materials. Recycling of these wastes is a tough problem due to
their high chemical resistance. The catalytic decomposition on nickel and its alloys is one of the
most promising methods for recycling Cl-containing organic wastes [1–4]. This method enables
the conversion of multicomponent waste to easily utilized HCl and carbon material [5]. The
forming carbon material represents fibers of different morphology, which have hydrophilic
properties and are characterized by a high specific surface area. These properties make them
promising for various applications [6], in particular, the development of heat-resistant materials
[7], composite materials with increased strength properties [8], the preparation of sorbents and
catalytic supports [9, 10].
Recent studies have shown that the decomposition process of Cl-containing organic wastes
can proceed on both highly disperse supported catalysts [5] and bulk materials (wire, mesh,
macrocrystalline powder) made of nickel or its alloys with transition metals [11]. The formation
of a carbon fiber during the reaction proceeds according to the carbide cycle mechanism [5, 12,
13]. This mechanism consists of the following steps: 1) catalytic decomposition of chlorinated
hydrocarbons on the metal particle surface; 2) diffusion transfer of carbon atoms through the of a
metal particle bulk; 3) formation of graphite-like phase nuclei and the growth of carbon fibers.
Spontaneous dispersion of bulk metal catalysts as a result of carbon erosion is a special
feature of the catalytic decomposition method [14]. In this case, catalytic particles (~ 200-250

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nm) form and detach from the initial catalyst. Then the particles are transferred into the formed
carbon fibers. This process provides high accessibility of the particle surface for the reagents and
promotes their long-term activity. As a result, a high yield of the carbon material is achieved [15,
16]. The basic features of the carbon erosion process were investigated during the catalytic
decomposition of 1,2-dichloroethane in the presence of hydrogen on massive nickel and various
nickel alloys (nichrome, chromel, etc.) [17]. It is shown that the concentration and type of
components in the alloy significantly influence the activity and resistance to oxidation and
deactivation of the formed catalytic particles.
We have previously demonstrated the possibility of preparing highly dispersed powders of
Ni1-xMx alloys (M = Cu, Co, Cr, Fe) in a wide range of compositions without alloying metals
[15, 16, 18]. In the synthesis of alloys, the thermolysis of multicomponent precursors (namely,
compounds or microheterogeneous mixtures) under reducing conditions was used. In the
precursors, the atoms of the alloy components are mixed. During the reduction of these
precursors in a H2 flow homogeneous alloy particles are formed. It has previously been shown
that in the 1,2-dichloroethane decomposition process the most active catalysts are nickel alloys
with metals capable to form non-stoichiometric carbides: MeCx. These carbides are solid
solutions in which carbon atoms are at interstitial positions in the metal host structure [13]. The
role of these carbides is related to the carbide cycle mechanism responsible for the catalytic
activity of metal particles in the process under study. Pd is a metal with a wide range of Pd–C
solid solutions [19]. In addition, dispersed palladium particles are known to catalyze the growth
of carbon nanofibers (CNFs) and nanotubes (CNTs) in the gas-phase decomposition of
hydrocarbons [20-23]. It should also be noted that heterogeneous catalysts based on metallic
palladium are characterized by high stability in a reaction medium containing chlorine
compounds (for example, HCl). Palladium is less subjected to deactivation under the influence of
HCl in comparison with traditional catalysts based on nickel, cobalt, and iron for the synthesis of
carbon material. Therefore, palladium catalysts are widely used in the reactions of liquid and gas
phase hydrodechlorination of polychlorinated hydrocarbons [24-27].
There are reasons to suppose that the introduction of a small amount of palladium (up to wt.
5%) into the composition of a nickel-based alloy can promote an increase in the catalytic activity
of nickel in the synthesis of carbon material (CM) and increase the catalyst stability in an
aggressive reaction medium containing hydrogen chloride. In this work, bimetallic porous
nickel-based Ni1-xPdx alloys with a Pd concentration in the range 1-10 wt.% were obtained. The
catalytic activity of alloys in the decomposition of 1,2-dichloroethane with the formation of a
carbon fibrous material was investigated. The characteristics of CM obtained were studied.
2. Materials and Methods
2.1. Reagents
For the synthesis of Ni1-xPdx alloys the following compounds were used: Ni(NO3)2ꢀ6H2O
(puriss.), K2[PdCl4] (puriss.), NaHCO3 (puriss.).
To carry out the catalytic experiments 1,2-dichloroethane (puriss.), argon (puriss. spec.) and
hydrogen (puriss. spec.) were taken. For catching hydrogen chloride gas a NaOH solution was
used.
2.2. Preparation of Ni1-xPdx solid solution
Weighed amounts of precursor salts K2[PdCl4] and Ni(NO3)2·6H2O calculated to obtain 1 g of
the alloy and taken in the required Ni:Pd ratio were dissolved in 100 mL of deionized water. The

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obtained solution of metal salts was added dropwise to an aqueous 0.1 M solution of NaHCO3
with vigorous magnetic stirring and elevated temperature (70 °C). During the synthesis рН was
maintained within 7.0–9.0 via a controlled addition of the precipitator: 1 M aqueous solution of
NaHCO3. The resulted grey green precipitate was centrifuged, washed abundantly with distilled
water, and dried at 105 °C for 12 h. Dried samples were then reduced in a hydrogen flow of 130
cm3/min at 800 °C for 30 min. Reduced Ni1-xPdx alloy samples were cooled down to room
temperature in a hydrogen flow. The cooled reactor was purged with helium. A pure Ni sample
was prepared as the reference in accordance with the procedure described above.
2.3. Characterization and measurements
The powder X-ray diffraction (XRD) analysis of the samples was performed at room
temperature on a Shimadzu XRD-7000 diffractometer (CuKα radiation, Ni filter on the reflected
beam). XRD patterns were recorded in the step mode in the angular range 2θ = 7–107°, step
0.05° (for the phase identification) and 2θ = 140–147°, step 0.02° (for the precise determination
of lattice parameter). Polycrystalline silicon (a = 5.4309 Å) was used as the external standard.
Data from the JCPDS data base were used as Ref. [28]. The lattice parameters were determined
by an angular position of the (331) reflection using the PowderCell 2.4 software. The
composition of Ni1-xPdx bimetal alloys was determined using a calibration curve constructed
based on lattice parameters of the known alloys. The volume-averaged crystallite sizes were
estimated from the integral broadening of the (111), (200), (220) peaks using the Scherrer
formula [29] and the WINFIT 1.2.1 program [30].
The morphology of synthesized Ni1-xPdx alloy and carbon nanomaterials (CNMs) was studied
by scanning electron microscopy (SEM) on a JSM-6460 (Jeol, Japan) electron microscope with a
resolution of 4 nm and magnifications from 5 × to 300,000. Transmission electron microscopy
(TEM) examinations were performed on a JEM-1400 (Jeol, Japan) instrument (accelerating
voltage 80 kV).
The SEM/EDX study of the Ni1-xPdx alloy precursor was carried out on a JSM-5100LV
microscope with an EX-23000BU energy-dispersive X-ray spectroscopy attachment at operating
voltage of 15 kV. The samples were compressed into tablets at 500 MPa prior to the test.
The chemical composition of synthesized Ni1-xPdx alloys was determined by atomic
absorption spectroscopy (AAS) on a Solaar IC-3000 spectrophotometer. Prior to the
measurement procedure, the samples were dissolved in nitric acid.
The textural parameters (SBET, m2/g; Vpore, cm3/g) of the obtained catalysts and CNM samples
were determined by low-temperature N2 adsorption (BET method). Nitrogen adsorption
isotherms were measured at 77 K on ASAP-2400 (Micromeritics, USA).
2.4. Study of the Ni1-xPdx catalytic activity
The kinetic measurement of the carbon product accumulation was conducted in a flow quartz
reactor equipped with McBain balances at 600 °C [31]. Prior to the catalytic experiment the Ni1-
xPdx alloy specimens were subjected to in situ reduction in a hydrogen stream at 500 °C for 30
min. The amount of each sample was 2.00±0.02 mg. After reduction the sample was brought to
contact with the reactant mixture containing a constant concentration of DCE vapor (7.5 vol.%),
H2 (37.5 vol.%) and argon (55 vol.%) as a balance. The total flow rate was 15 L/h. HCl released
to the gas phase was trapped at the reactor outlet with a NaOH solution.
3. Results and Discussion

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3.1. Synthesis of Ni1-xPdx
Mixed nickel-palladium hydroxycarbonates were used as multicomponent precursors for the
preparation of alloys. These precursors were obtained by the combined precipitation of Ni(NO3)2
and K2[PdCl4] from an aqueous solution. The precipitation was carried out with a NaHCO3
solution at its constant excess. At the same time, due to supersaturation, hydroxycarbonates of
both metals precipitate simultaneously. As a result, a high degree of mixing of Ni and Pd in the
obtained product is achieved. The structure determination and the phase composition of the
obtained precursor were impossible since it was amorphous. Combined SEM/EDX method
reveals that this method of alloy synthesis has a significant advantage over mechanical grinding
of the precursors (Fig. 1). We studied two samples: 1) precursor obtained by grinding of
Ni(NO3)2·6H2O and K2[PdCl4] in a mortar; 2) precursor synthesized by our method (sediment).
To obtain the map of regions enriched and depleted in palladium (Fig. 1) for both precursors, the
SEM/EDX method was used. The size of these regions varies from 10 to 200 ꢁm in the grinded
sample, and from 2 to 10 ꢁm in the sediment. In addition, in sediment these regions are located
much more evenly than in the grinded sample. Thus, it is clearly shown that in grinded samples
the necessary extent of homogenization of the substances is not achieved.
(a)
(b)
Fig. 1. SEM/EDX data of Ni1-xPdx alloy precursors (10 wt.% Pd) before reducing: a) grinding
of alloy precursors in a mortar; b) sediment obtained by our technique.
When the dried precursor was reduced in an H2 atmosphere at 400, 500, 600, and 800 °C,
powders of differently dispersed Ni1-xPdx alloys formed. According to the elemental analysis
(AAS) data, the composition of prepared alloys strictly corresponds to the preset alloy
composition in the synthesis (Fig. 2). The crystallite size in the obtained alloys depends on the
synthesis temperature. In the SEM images of the obtained samples, porous structures with
different morphologies are observed (Fig. 3). Thus, at a temperature of 400 °C, a porous
structure constructed of coupled bridges with a diameter of ~ 200 nm was obtained (Fig. 3a, b).
With an increase in the temperature to 500, 600, and 800 °C, the diffusion rate of Ni and Pd
atoms increases significantly, consequently, the crystallites enlarge. At T = 500 °C, the bridges
are sintered into small blocks consisting of grains with a diameter of 200-300 nm (Fig. 3c, d). At
600 °C the blocks are sintered even more with an increase in the grain diameter to 500-600 nm
(Fig. 3e, f). The alloys obtained by calcination of the precursor samples at 800 °C consist of 1-2
ꢁm grains (Fig. 3g, h). Despite that with increasing calcination temperature the alloys are close
in structure to bulk materials, they are still dispersed powders. The crystallite size of the obtained

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samples, determined from the XRD data, varies from 30 nm at T = 400 °C to 100 nm at 800 °C
(Table 1).
Fig. 2. Correspondence between the composition of synthesized alloys (according to AAS
data) and the preset alloy composition in the synthesis.
(a)
(b)
(c)
(d)

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(f)
(e)
(g)
(h)
Fig. 3. SEM micrographs of Ni1-xPdx alloys (5 wt.% Pd) synthesized at 400 °C (a, b), 500 °C
(c, d), 600 °C (e, f), and 800 °C (g, h).
Table 1. Characteristics of the obtained Ni1-xPdx samples.
№
Synthesis
temperature, composition,
Preset
Composition
by AAS,
XRD data
°С
wt. % Pd
wt.% Pd
a, Å
Composition, Composition, Crystallite
at.% Pd
wt.% Pd
size, nm
1
2
400
500
600
800
800
800
800
800
800
800
5
5
4.2
5.3
5.2
1.1
2.0
2.8
4.4
5.0
6.4
9.6
3.539(1)
3.536(1)
3.537(1)
3.527(1)
3.529(1)
3.532(1)
3.536(1)
3.538(1)
3.543(1)
3.551(1)
2.5
4.4
27
2.7
2.8
0.7
1.2
1.7
2.7
3.6
3.9
5.5
4.8
5.0
1.3
2.2
3.0
4.8
6.3
6.9
9.5
36
62
76
100
81
60
73
50
82
3
5
4
1
5
2
6
3
7
4
8
5
9
6
10
10
3.2. Powder XRD analysis

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In the diffraction patterns of all samples within 2θ= 40-100º, a set of reflections typical of a
face-centered cubic (fcc) lattice is observed (Fig. 4a). Impurity peaks are absent. The position of
the reflections is shifted to the low-angle range with respect to pure nickel. The shift of the
reflections is most pronounced in the far-angle range (Fig. 4b).
(b)
(a)
Fig. 4. XRD profiles for Ni1-xPdx alloys: (a) survey patterns; (b) (331) reflections in the far
angle range.
The XRD qualitative data of the obtained alloys are summarized in Table 1. As can be seen,
an increase in the Pd content in the alloy leads to a consistent increase in the lattice parameter of
the solid solution. The lattice parameters of synthesized solid solutions fit well with the graph of
the dependence of lattice parameters on the chemical composition of the Ni1-xPdx alloy (Fig. 5),
which is constructed from the literature data [32-34]. This calibration reveals an insignificant
deviation from Vegard’s law [35] and in the low concentration range is close to linear. The
composition of solid solutions based on the Ni crystal lattice, which is determined from the XRD
data, is in good agreement with the nominal content of metals in the samples (AAS data). These
data, as well as the absence of impurity peaks in the diffraction patterns, indicate that the
obtained alloys are homogeneous.
Fig. 5. Dependence of the lattice parameter of Ni1-xPdx alloy upon the nickel atomic fraction
(XNi): experimental (□) and literature (○) data.

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3.3. Catalytic properties of Ni1-xPdx alloys in the decomposition reaction of 1,2-
dichloroethane
A sample of Ni1-xPdx containing 5 wt.% of Pd was investigated in a decomposition of 1,2-
dichloroethane with producing of carbon material. As a result of contact of the sample with
C2H4Cl2 vapors in excess H2, a rapid disintegration of a massive alloy occurs with the
appearance of submicron metal particles. These particles catalyze the growth of carbon
filaments. The phase of disintegration of the alloy is characterized by an induction period (10–20
min). After the induction period, a rapid growth of the carbon product takes place. The activity
of the catalyst forming in this way can be represented as the yield of the carbon product (in
grams) over a certain time, referred to 1 g of alloy.
The results of comparative catalytic tests are shown in Fig. 6. The same figure presents for
comparison the previously published catalytic data [15] obtained for 100% Ni (reference
sample), Ni1-xCox, and Ni1-xCux samples. These samples were prepared by a similar method. It
can be seen that after two hours of the experiment the Ni1-xPdx catalyst activity is slightly higher
than that of other samples. However, the advantage of using palladium as a promoting additive to
nickel becomes evident in 3 hours from the start of the process (Fig. 6). A further increase in the
experiment time to 5 hours showed that the Ni1-xPdx system retained a high catalytic activity in
the synthesis of CM. By this time, samples based on Ni, Ni1-xCox and Ni1-xCux are completely
deactivated when CM is accumulated in an amount of 40-50 g/gcat [18]. After the 5-hour reaction
the yield of the carbon product was almost 160 g/gcat for the Ni1-xPdx catalyst, which is more than
3 times better than the efficiency of the reference samples.
Fig. 6. Yield of CM obtained by decomposing the DCE/H2/Ar reaction mixture on Ni, Ni1-
xCux, Ni1-xCox, and Ni1-xPdx catalysts for 2, 3, and 5 hours. The process temperature is 600 ° C.
Thus, the introduction of a small amount of palladium into the nickel alloy, resistant to the
poisoning effect of hydrogen chloride, contributes to a sharp increase in the catalyst stability.
This property is expressed in the absence of deactivation of the Ni1-xPdx catalyst in resource
tests. Due to this, a high yield of CM exceeding 100 g/gcat may be achieved.
The structure and morphology of the carbon product obtained as a result of the 1,2-
dichloroethane decomposition on a Ni1-xPdx catalyst was investigated by SEM and TEM. The
characteristic images are shown in Fig. 7. It can be seen that on the catalyst CM is formed only

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in the form of long carbon filaments of a submicron diameter which grow by conventionally
parallel beams. The average diameter of carbon fibers is in the range 0.2–0.9 ꢁm. The formation
of carbon filaments is preceded by the process of complete destruction of the initial massive
alloy. As a result of this destruction, dispersed active particles are formed (Fig. 7b). It should be
noted that the special character of the growth of the carbon phase on Ni1-xPdx catalysts leads to
the formation of a product with an extremely low bulk density of less than 0.03 g/cm3. At the
same time, for CMs synthesized on the other analogous Ni1-xMx (M = Co, Cu, Fe) catalysts this
parameter varies in the range 0.08–0.15 g /cm3.
(a)
(b)
Fig. 7. Filamentary morphology of the carbon product: (a) SEM data and the structure of
carbon filaments, (b) TEM data. The sample was obtained by decomposing a C2H4Cl2/H2/Ar
mixture on a Ni1-xPdx catalyst (5 wt.% Pd) at 600 °C.
Metal particles playing the role of active centers of CM growth are located in the mass of the
carbon product formed. Most often, the formation of a graphite-like phase on the surface of an
active particle occurs immediately in several directions. Fig. 7b shows an active particle
catalyzing the simultaneous growth of four carbon filaments. Usually, carbon fibers have a
pronounced segmented structure [16] (Fig. 7b). This fact indicates a discrete character of carbon
deposition. Due to a high degree of structure defectiveness, obtained CM has a high specific
surface area (up to 580 m2/g) and a developed pore system with a volume of 0.5–0.6 cm3/g.
4. Conclusions
By reductive thermolysis of multicomponent precursors highly dispersed binary Ni1-xPdx
alloys are synthesized. The proposed method makes it possible to obtain solid solutions with a
preset composition in the concentration range 1-10 wt.% Pd. It is established that the
introduction of a small amount of palladium into the nickel alloy contributes to a noticeable
increase in the catalyst stability, which is expressed in the absence of its deactivation in resource
tests. After the 5-hour reaction the yield of the carbon product was 160 g/gcat for the Ni1-xPdx (5
wt.% Pd) catalyst. Thus, the obtained alloys can be successfully used as catalysts for the catalytic
decomposition of DCE to produce a carbon product.
Acknowledgements
This study was supported by Ministry of Science and High Education (Project № АААА-
А17-117040610364-9 and Project № АААА-А17-117041710086-6).
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Highlights
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A new procedure for synthesis of highly dispersed Ni1-xPdx alloys is proposed.
The particle size of the alloys depends on the synthesis temperature.
Ni1-xPdx shows high stability in the carbon fiber formation reaction.
Carbon fiber is characterized by high morphological uniformity.