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Energy Procedia 39 (2013) 387 – 395

Asian Nuclear Prospects 2012

(ANUP2012)

Study on Electrochemical Properties of Palladium in Nitric

Acid Medium
Shengchu Liua, Ruiqin Liua, Yan Wua, Yuezhou Weia,*, Baizeng Fangb
a
School of Nuclear Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, People’s Republic of China
b
Department of Chemical & Biological Engineering, University of British Columbia, 2360 East Mall, Vancouver, B.C.,
Canada V6T 1Z3

Abstract

The electrochemical behavior of palladium (II) in nitric acid was studied using various electrochemical
techniques. The cyclic voltammogram of palladium (II) recorded at Pt electrode presented a series of
electrochemical reactions corresponding to the redox behavior of palladium. SEM images of palladium
obtained by electrolysis revealed the dendrite growth, which was uniform all over the entire surface of Pt
electrode. The recovery ratios of palladium at different nitric acid concentrations were high, and the
Faradic efficiency decreased as the nitric acid concentration was increased, which might be due to the
reduction of nitric or H+ ions. The reduction of palladium (II) was irreversible and stirring during
electrolysis could improve the electrodeposition rate.

© 2013
© 20xxTheThe Authors.
Authors. Published
Published by Elsevier
by Elsevier Ltd.
Ltd. Open access under CC BY-NC-ND license.
Selectionand
Selection and/or peer-review
peer-review under responsibility
under responsibility of Institute of Instituteand
of Nuclear ofNew
Nuclear and
Energy New Energy
Technology, Technology,
Tsinghua University
Tsinghua University

Keywords: Palladium; Fission product; Electrochemical techniques; Electrodeposition

* Corresponding author. Tel.:+86-21-34205684; fax: +86-21-34205182.

E-mail address: yzwei@sjtu.edu.cn.

1876-6102 © 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and peer-review under responsibility of Institute of Nuclear and New Energy Technology, Tsinghua University
doi:10.1016/j.egypro.2013.07.227
388 Shengchu Liu et al. / Energy Procedia 39 (2013) 387 – 395

1. Introduction

Palladium is a noble metal. Owing to its irreplaceable physical and chemical properties, such as high
ductility, strong hydrogen adsorption capability [1] and excellent catalytic properties [2], there is a huge
demand for palladium and its compounds in various industrial fields [3]. The natural abundance of
palladium in the earth’s crust is very low (1×10-6 %) and only occurs in a few countries. All the mines are
likely to be consumed in another few decades at its current rate of use [4]. The price of palladium is rising
steadily every year on the world market, and predictably, will keep rising in the long run due to the
growing mining costs.
Palladium and other platinum group metals (PGMs) namely, ruthenium, rhodium are produced as man-
made precious metal after nuclear fissions [5]. At a burn up of 33 GWd/t (gigawatt days per metric ton),
one metric ton of spent fuel contained more than 1 kg palladium. It’s estimated that by 2030 spent nuclear
fuel could provide as much as 1000t palladium. This would be a considerable addition to the yield from
natural sources [6]. Fission palladium is comprised of isotopes 104 (17 wt.%), 105 (29 wt.%), 106 (21
wt.%), 107 (17 wt.%), 108 (12 wt.%), and 110 (4 wt.%). Among them, Pd-107 is the only radioactive
isotope with a half-life of 6.5×106 years. Since the maximum energy of -ray emitted by Pd-107 is 35
KeV [5] and the radiation intensity at the surface of fission palladium is only merely 520 Bq•cm-2. Thus,
if recovered, its weak radioactivity can be tolerated for many industrial applications [7]. On the other
hand, in the process of vitreous solidification for HLLW, short for nuclear high level liquid waste, PGMs
are harmful, and so far, Rokasho reprocessing plant in Japan has been compelled to stop running because
they formed separate phases, causing deterioration in the stability of the glass, which is very adverse to
the storage of vitreous solidification [8].
Based on these facts, to separate and recover PGMs, especially palladium, from HLLW has been one
of the focused research topics in the field of radiochemistry in the past few decades [7]. Solvent
extraction and ion exchange are the most studied methods for the recovery of palladium from nitric acid
solutions worldwide [3], which have been described by many documents [9-11]. In comparison with
solvent extraction, electrochemical approaches are reported as the most promising methods because of
their simplicity, cost effectiveness, accessibility to recover palladium from acid solution and no need of
external reagents [12]. The rate of cathodic deposition of palladium from nitrate solutions and the current
efficiency of the process were studied by Kirshin et al [13]. However, very little work was reported about
the detailed electrochemical behavior and kinetic parameters of palladium (II) in nitric acid medium. In
this study, we intend to clarify the electrochemical behavior of palladium (II) in nitric acid by using
various electrochemical techniques. Electrowinning of palladium under different voltages and effect of
nitric acid concentration were also investigated.

2. Experimental

All the chemical agents used in the study are of analytical grade and used without any further
purification. Pd(NO3)2•2H2O was procured from ACROS, Belgium. The Pd(II) in nitric acid media was
made by dissolving a required quantity of Pd(NO3)2•2H2O in appropriate concentration of nitric acid.
A UV-Vis spectrometer (UV-3600, Shimadzu, Japan) was used to record the absorption spectrum of
palladium (II) in various concentrations of nitric acid. Electrodeposition studies were carried out in a
single-chamber electrolysis cell in which the temperature was controlled by an electric-heated
thermostatic water bath with built-in magnetic stirrer which could provide stirring during electrolysis. In
all the electrochemical measurements, platinum plate (surface area= 8cm2), platinum wire and Ag/AgCl
electrode acted as working, counter and reference electrodes, respectively. All the electrochemical studies
were controlled with a potentiostat (CHI 660D, Shanghai Chenhua Electric Co, China). The
 Shengchu Liu et al. / Energy Procedia 39 (2013) 387 – 395 389

concentrations of palladium present in aqueous phase before and after electrolysis at different time points
were determined by an inductively coupled plasma atomic emission spectrometry (ICP-AES) instrument
(ICP-7510, Shimadzu, Japan). After the electrodeposition, the platinum plate was washed extensively
with deionized water and dried in a vacuum drying oven for surface characterization. A scanning electron
microscope (SU-1510, Hitachi, Japan) working at 10kV was used to examine the surface morphology.

3. Results and Discussion

3.1. The UV-vis absorption patterns

0.180

0.135
Absorbance

9M
0.090 6M
3M
1M
0.1M

0.045

0.000

360 420 480 540 600

Wavelength nm

Fig. 1. UV-vis absorption patterns of palladium (II) in various concentrations of nitric acid. [Pd]=0.5mM

Figure.1 shows the absorption spectra of palladium (II) in various concentration nitric acid (ranging
from 0.1M to 9M), the absorption peaks exhibit a red-shift and the peak value increases as the
concentration of nitric acid increases. This is caused by the formation of different nitrato-complexes. This
is caused by the formation of different nitrato-complexes. Tarapcik et al[14] reported that [Pd(H2O)4]2+,
[Pd(NO3)(H2O)3]+, [Pd(NO3)(H2O)2] and [Pd(NO3)(H2O)]- are the four main species in HNO3 solution,
their stability constants are 3.28, 2.13, 0.223 and 0.004, respectively. However, by using UV/Vis
absorption spectrophotometry, Toshiyuki Fujii et al[15] found that the major palladium species were
Pd2+,[Pd(NO3)]+ and Pd(NO3)2, and the stability constants of [PdNO3]+ was calculated to be
1=1.32(HNO3=1M), 1.49(HNO3=3M), or1.47(HNO3=5M), and that of Pd(NO3)2 to be 2=0.45
(HNO3=3M) or 0.14(HNO3=5M). On the whole, the proportion of palladium anion species rises with the
increase of nitric acid concentration.

3.2. The cyclic voltammogram

The cyclic voltammogram of palladium (II) in 3M nitric acid recorded at 298 K is shown in Fig.2, the
sweeping rate of which is 20 mV/s.
390 Shengchu Liu et al. / Energy Procedia 39 (2013) 387 – 395

Current, mA
-1

-2

-3

-4

-5
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Potential, V

Fig. 2. Cyclic voltammogram of 5mM palladium (II) in 3M HNO3 at 298 K; Scan rate: 20 mV/s. (Unit: Potential, V vs Ag/AgCl)

Within the scanning potential range of 0.175 ~ 1.2V (vs. Ag/AgCl), there are two sharp oxidation
peaks and three sharp reduction peaks, all of which associate with palladium. On the negative-going
forward scan, the first peak located at ca.0.3V ( ) is due to the reduction of palladium (II) into palladium
(0), shown as Eq. (1). A weak reduction wave starting from ca. 0 V and a strong reduction peak observed
at ca. 0.125V ( ) correspond to weak and strong adsorption of H respectively on metallic palladium
formed, as described in Eq. (2). Hydrogen evolution reaction ( ), shown as Eq. (3), begins at 0.17 V,
where a large amount of tiny bubbles occurs. On the positive-going reverse scan, a large oxidation peak
occurs at 0.08V( ) and a weak oxidation wave starting at ca. 0.062 V suggest the desorption of H from
palladium, as described in Eq. (4). A surge in anodic current occurring at a potential of 0.4V, which
culminates in a peak at ca. 0.71V, con¿rms the oxidation of palladium (0) into palladium (II) as expressed
by Eq.(5). Evidently, the cyclic voltammogram of palladium (II) provides us with a series of
electrochemical reactions corresponding to redox behavior of palladium and the possibility to recover
palladium in metallic form by direct electrolysis from nitric acid.
Pd 2 Pd 0 (1)
Pd xH xe- PdHx (2)
2H H2 (3)
PdHx Pd xH xe- (4)
Pd 0 Pd 2 (5)
In order to investigate the influence of HNO3 concentration, cyclic voltammogram measurements of
5mM Pd (II) in 0.1M, 1M and 3M HNO3 were conducted at 298 K.
Within the scanning potential range of -0.1 ~ 1V (vs. Ag/AgCl), in all three cases, one reduction peak
(Eq. (1)) and one reduction peak( Eq. (5))could be get on the negative-going and positive-going forward
scan, respectively. From Fig.3, the redox peak currents reduced as HNO3 concentration increases, this
may be caused by the decrease of diffusion coefficients of Pd complexes which change with the HNO3
concentration as we discussed. Moreover, when HNO3 concentration increases from 0.1 to 3 M, the
reduction peaks shifted negatively and the peak potentials separation for the redox reactions increased
from 295mv to 461mv. Obviously, low HNO3 concentration is electrochemically favourable for the
 Shengchu Liu et al. / Energy Procedia 39 (2013) 387 – 395 391

reduction of palladium (II) for the reason that we can get a higher reduction current and the reduction
reaction could proceed in a relatively high potential.

2.7

1.8

0.1M

Current, mA
1M
0.9
3M

0.0

3M
-0.9 1M
0.1M

-1.8
0.2 0.4 0.6 0.8 1.0
Potential, V

Fig. 3. Cyclic voltammogram of 5mM palladium (II) in 0.1M, 1M and 3M HNO3 at 298 K;
Scan rate: 20 mV/s. (Unit: Potential, V vs Ag/AgCl)

3.3. Sampled-current voltammetry of palladium (II)

3
Current, mA

2 Ep
E3/4

E1/4
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Potential, V

Fig. 4. Sampled-current voltammetry curve of palladium (II) in 3M HNO3 solution at 298K (Unit: Potential, V vs Ag/AgCl).

Potential step method was employed to get sampled-current voltammetry. A representative sampled-
current voltammetry curve is shown in Fig.4 for palladium (II) in 3M HNO3 solution, the initial potential
of which was 1.2 V, the sampling time was 0.2 s. According to Tomes criterion [16], the value of |E3/4 -
392 Shengchu Liu et al. / Energy Procedia 39 (2013) 387 – 395

E1/4| is much larger than the value required for a reversible process, which means that the reduction of
palladium (II) in nitric acid at Pt electrode is irreversible and the process is not only controlled by
diffusion but also charge transfer kinetics.

3.4. Electrowinning of palladium

Figure. 5 shows the comparison of recovery ratio for the electrodeposition of palladium during
electrolysis in 3M HNO3 medium at three different potentials. Controlled potential electrolysis of a
solution of palladium (II) (5mM) in 3M HNO3 were performed at three different potentials ( 0.3 V, 0.2
V, 0.1V vs. Ag/AgCl) on Pt plate (8 cm2) as cathode with a 4h electrolytic time in all cases. The
selections of voltage were based on the information provided by cyclic voltammogram (Fig. 2). As shown
in Fig. 8, the curves obtained at 0.2 V and 0.1 V are close to each other while a much higher recovery
ratio was observed when 0.3 V was applied in electrolysis. In the later case, many small bubbles were
clearly observed in the beginning of electrolysis, which stirred the bulk solution and accelerated the
electrodeposition rate of palladium and gradually decreased over time. After 4h electrolysis, the recovery
of palladium was quantitative, and the recovery ratio of which at 0.3 V, 0.2 V and 0.1V are 100%,
50% and 47%, respectively.

100

-0.3V
-0.2V
-0.1V
75
Recovery ratio, %

50

25

0
0 1 2 3 4
Time, h

Fig. 5. Recovery ratio for the electrodeposition of palladium from 3M HNO3 at different applied potential at 298 K (Unit: Potential,
V vs Ag/AgCl)

The influences of nitric acid concentration on the cathodic deposition of palladium (II) (5mM) were
investigated at a constant applied potential of 0.1V, and the results are shown in Fig. 6.
When there is no stirring, the curves obtained from 1M and 3M HNO3 are close to each other and a
slightly higher curve was got from 0.1M. However, the mean current efficiency for the electrodeposition
of palladium from 0.1M, 1M and 3M HNO3 are 65%, 51% and 29%, respectively. The current efficiency
of electrolysis decreases as the nitric acid concentration increases, which could be due to the reduction of
nitric acid or H+ ions. When stirring was introduced during electrolysis in 3M HNO3, the
electrodeposition rate of palladium increased substantially, and near 100% recovery ratio of palladium
was achieved within 2 h. Evidently, stirring could greatly increase the electrodeposition rate of palladium
in from nitric acid solutions.
 Shengchu Liu et al. / Energy Procedia 39 (2013) 387 – 395 393

100

3M stirring
3M
80 1M
0.1M

Recovery ratio, %
60

40

20

0
0 1 2 3
Time, h

Fig. 6. Recovery ratio for the electrodeposition of palladium from 0.1M, 1M and 3M (with and without stirring) HNO3 at -0.1V. ; T
= 298 K (Unit: Potential, V vs Ag/AgCl)

×200 ×1000

×3000 ×5000

Fig. 7. SEM images of palladium obtained by electrolysis at Pt electrode in 3M HNO3 at different magnifications.
394 Shengchu Liu et al. / Energy Procedia 39 (2013) 387 – 395

The deposit obtained from the electrolysis in 3M HNO3 was subjected to surface morphological
examination by scanning electron microscopy (SEM). As shown in Fig. 7, a thick but uniform
electrodeposition of palladium was observed all over the surface of Pt electrode. The clear dendrite
morphology of palladium electrodeposition shows free dendrite growth, thin dendrite arms as well as side
branch. The deposit was loose and could be scraped off from Pt plate easily, offering us the convenience
to recover metallic palladium from nitric acid media after direct electrolysis.

4. Conclusions

In this work, the electrochemical behavior of palladium (II) in nitric acid medium at platinum electrode
was investigated using various electrochemical techniques. UV-vis absorption curves demonstrated that
palladium (II) in various concentration nitric acid had optical absorbance ranging from 400~450 nm and
showed a spectral red-shift resulting from the formation of different nitrato-complexes. By analyzing the
cyclic voltammogram of palladium (II) in nitric acid, a series of electrochemical reactions associated with
palladium were recognized. According to Tomes criterion, the reduction of palladium (II) in nitric acid at
Pt electrode was irreversible, SEM images of palladium obtained by electrolysis reveal the dendrite
growth in all cases, which is uniform all over the entire surface of Pt electrode. The recovery ratios of
palladium at different nitric acid concentration were high, and the faradic efficiency of electrolysis
decreased with increasing nitric acid concentration, which is probably due to the reduction of nitric or H+
ions. Stirring could facilitate the reduction of palladium (II) in relatively low nitric acid concentration.

Acknowledgements

Projects supported by the Major Research Plan of the National Natural Science Foundation of China
(No. 91026019 and No. 91126006).

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