Journal of The Electrochemical

Society

OPEN ACCESS You may also like

- Role of Iron Impurity in Hydrometallurgical
A Selective Separation of Platinum Group Metals Recovery Process of Spent Lead-Acid
Battery: Phase Transformation of Positive
from the Fe-PGM Alloy Using Electrodeposition Material Made from Recovered Leady
Oxide
Wenhao Yu, Jiakuan Yang, Sha Liang et
Combined with Electrochemical Dealloying al.

- Hybrid Hydro-pyrometallurgical Process

To cite this article: Przemysław Łoś et al 2024 J. Electrochem. Soc. 171 012506 for Zn Recovery from Electric Arc Furnace
Dust
R.A. Bayoumi, N. M. Abdelmonem, M. A.
Soliman et al.

- The importance of sample preparation in

View the article online for updates and enhancements. the hydrometallurgical processing of
refractory gold concentrates
S A Ivanik, D A Ilyukhin and A V Shalygin

This content was downloaded from IP address 65.60.244.183 on 30/04/2024 at 14:57

 Journal of The Electrochemical Society, 2024 171 012506

A Selective Separation of Platinum Group Metals from the

Fe-PGM Alloy Using Electrodeposition Combined with
Electrochemical Dealloying
Przemysław Łoś,1 Sabina Jacek-Krakus,1 Justyna Markowicz,1 Adrian Łabuz,1
Agnieszka Sobianowska-Turek,2 Michał Zygmunt,1 Michał Janosz,1 and
Agnieszka Fornalczyk3,z
1
Elemental Strategic Metals Sp. z o.o., 05-825 Grodzisk Mazowiecki, Poland
2
Wrocław University of Science and Technology, Faculty of Environmental Engineering, 55-370 Wrocław, Poland
3
Silesian University of Technology, Faculty of Materials Engineering,40-019 Katowice, Poland

In the European automotive industry, a considerable volume of recalled car catalysts stems from diesel vehicles, characterized by
their high silicon carbide (SiC) content. Processing such materials poses notable challenges compared to gasoline vehicle catalysts.
The presence of SiC demands additional time and energy in electric arc furnace processing, with SiC’s high melting point and
strong reducing properties complicating separation. The Fe-PGM alloy obtained after pyrometallurgical treatment of these SiC-rich
catalysts presents hurdles for hydrometallurgical processing. With high silicon content, the alloy resists corrosion in sulfuric acid,
impeding solubility and hindering progress in the recovery process. This article explores an innovative approach for selectively
extracting platinum group metals (Pt, Pd, Rh) from Si-rich Fe-PGM alloys. Traditional hydrometallurgical methods struggle due to
the alloy’s near-immunity to acid leaching. The study presents chemical leaching results and proposes electrodeposition combined
with electrochemical dealloying as a feasible solution. This method, aiming for selective metal separation, seeks to enhance
recovery process profitability by producing pure metals.
© 2024 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited. This is an open access
article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/
by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/
1945-7111/ad1d96]

Manuscript submitted December 5, 2023; revised manuscript received January 5, 2024. Published January 24, 2024. This paper is
part of the JES Focus Issue on Pulse Electrolysis, Industrial Electrochemical Engineering, and Scale-Up: In Honor of E. Jennings
(EJ) Taylor.

Catalytic converters are a crucial component in modern car,
playing a vital role in reducing harmful emissions from the exhaust
system. These converters contain precious metals such as Platinum,
Palladium, and Rhodium, which have high economic value and are
in limited supply worldwide. The recovery of these metals from used
catalytic converters can provide a solution to the challenges of
increasing resource efficiency and reducing waste, as well as
contributing to a more sustainable future.
However, the recovery of precious metals from used catalytic
converters is a complex process that involves many technical
difficulties. The precious group metals (PGMs - Pt, Pd, Rh) used
in catalytic converters are resistant to corrosion and difficult to
extract, making the recovery process challenging. Additionally, the
limited amount of precious metals available worldwide means that
the recovery of these metals must be maximized to reduce waste and
increase resource efficiency. The recovery process must also
consider the environmental impact of the operation. The improper
disposal of catalytic converters can result in the release of harmful
pollutants, which can have a negative impact on the environment and
public health. Therefore, it is crucial that the recovery process be
designed with environmental considerations in mind, to ensure that it
is both safe and sustainable.
Catalysts are used in the automotive industry to convert harmful
emissions from vehicle engines into less harmful ones. This is
achieved through the reduction of nitrogen oxides into nitrogen, as
well as the oxidation of hydrocarbons and carbon monoxide into
carbon dioxide.1 The catalysts typically contain precious metals such
as palladium, platinum, and rhodium. Catalytic converters are made
up of honeycomb-like structures that house these precious metal
catalysts on their large surface areas. The concentration of these
metals in a single catalytic converter can vary widely depending on
the manufacturer. For example, modern car catalytic converters may
contain anywhere from 300 to 1000 micrograms of platinum per
z
E-mail: Agnieszka.Fornalczyk@polsl.pl
gram, 200 to 800 micrograms of palladium per gram, and 50 to 120
micrograms of rhodium per gram.2
The recovery of precious metal (PGMs) from catalysts involves
several stages, including pretreatment, enrichment, extraction, se-
paration and purification, and reduction to metal products.
Regardless of the chosen recovery method, a pretreatment stage is
typically required. This stage includes mechanical processing, such
as collection, cleaning and crushing, to remove residual materials.3
The enrichment of PGMs on an industrial scale can be achieved
through the use of pyrometallurgical, hydrometallurgical, or a
combination of both methods. In the pyrometallurgical process,
PGMs are separated from other materials through smelting, with the
use of fluxes and reductants. In hydrometallurgical processes, PGMs
are extracted through the use of oxidizing leaching systems such as
hydrogen peroxide, acids like hydrochloric acid, sulfuric acid, and
nitric acid, bases such as sodium hydroxide and sodium hypo-
chlorite, and complexing agents like cyanide and thiosulfate.3
Separating individual Platinum Group Metals (PGMs), such as
Pt, Pd, and Rh, after they have been dissolved into solution is a
complex process due to their close chemical similarities. These
metals have similar physical and chemical properties, making it
difficult to separate them effectively. However, the profitability of
the recovery process is largely dependent on the purity of the
individual metals. In order to obtain maximum profits, it is important
to carry out efficient separation processes. Techniques such as ion
exchange chromatography, solvent extraction, electrochemical pro-
cesses and distillation are commonly used to separate the individual
PGMs. Despite these methods, the separation of these metals
remains a challenging task in the field of PGMs recovery.
The electrochemical processes such as electrodeposition and
electrochemical leaching or electrochemical dealloying offer several
benefits for the separation of platinum group metals (PGMs) from
spent automotive catalysts. The use of electrodeposition enables the
recovery of high-purity PGMs, as impurities can be effectively
removed through the control of the deposition conditions.
Additionally, electrodeposition is a relatively low-cost method and
can be easily scaled up for industrial use, making it a cost-effective
 Journal of The Electrochemical Society, 2024 171 012506
Figure 1. Exemplary anode sample made of Fe-PGM alloy that contain high
amount of silicon (Si).
option for PGMs separation and recovery. Furthermore, the process
is highly efficient and can be carried out at room temperature, which
helps to minimize energy consumption. The process also has a high
recovery rate, which maximizes the yield of PGMs, reducing waste
and improving the overall sustainability of the recovery process.
Thus, electrodeposition processes offer a simple, cost-effective, and
efficient solution for the separation of PGMs contained in spent
automotive catalysts. In the current study we applied electrodeposi-
tion combined with electrochemical leaching/dealloying in one
stage, which make the process even more efficient.
Electrochemical dealloying is a well-known process, which has
recently raised quite a wide range of interests in new applications
especially, related to the manufacturing of catalysts and
electrocatalysts.4 On the other hand, the studies of electrolytic
recovery using electrochemical dealloying (of less noble metal i.e.
Fe) of PGMs from Fe-PGMs alloy are very rare.5 Although there are
many reports on the electrochemical dissolution of pure PGM
metallic electrodes, there are only a few papers published on the
subject of electrochemical dissolution of ternary Pt-Pd-Ru noble
metal alloys.6
On the European market, a significant portion of the recalled car
catalysts, come from diesel vehicles due to their high silicon carbide
(SiC) content. According to industry sources in the platinum metals
recovery sector, processing this type of material is more challenging
compared to those from gasoline vehicles. BASF Corp. reports that
the SiC streams in spent emission control catalysts require additional
time and energy to be processed in an electric arc furnace, as
compared to cordierite ceramic materials. Furthermore, SiC has a
Table I. ICP-OES analysis results (in %) of Fe-PGM alloy obtained in reduction melting in an electric furnace.
Composition % Fe Cr Cu Si
Fe-PGM alloy 63.15 9.18 0.30 14.72
Figure 2. The results of reductive leaching of selected elements of the Fe-
PGM alloy in 20% H2SO4.
very high melting point of over 2700 °C, and acts as a strong
reducing agent during melting, making it difficult to separate. Its
high density of 3.2 g cm−3 also creates a dense layer between the
slag and the metal, which makes it harder to process. As a result,
most recyclers avoid processing catalysts containing SiC, and the
material is separated from cordierite at the purchasing stage. From a
hydrometallurgical processing perspective, the Fe-PGM alloy ob-
tained after pyrometallurgical remelting of used car catalysts with a
high content of silicon carbide (SiC) presents significant challenges.
The presence of iron-silicon with over 14.7% silicon in the alloy
makes it highly resistant to corrosion in sulfuric acid, severely
hindering its solubility and making it difficult to advance to the next
stage of the recovery process. This resistance to corrosion in sulfuric
acid, a commonly used leaching agent, poses a major challenge in
the successful completion of the hydrometallurgical process and
affects the overall efficiency and effectiveness of the recovery
process. The trend shows that the share of such raw materials will
increase to over 30% by 2025, and the processing of this type of
catalyst will be increasingly important.7
The aim of the article is to present a new and innovative approach
for the selective separation of platinum group metals (Pt, Pd, Rh)
from Fe-PGM alloys that contain high amounts of silicon (Si). The
challenge with processing these alloys by conventional hydrome-
tallurgical methods is that the high content of silicon makes the alloy
almost completely resistant to corrosion and leaching in acids.
Results concerning chemical leaching of Fe-PGM alloys that contain
high amounts of silicon (Si) are presented and discussed in this
paper. The article proposes the use of electrodeposition combined
with electrochemical dealloying (ED) in one process stage (feasi-
bility studies) as a viable solution to the problem of such alloys
treatment. Electrodeposition combined with electrochemical deal-
loying (ED) is a method in which metal ions are deposited onto a
substrate in a controlled manner, producing a metal film or layer. By
using this process, the Authors aim to achieve a selective separation
of platinum group metals from the Fe-PGM alloy, improving the
profitability of the recovery process by producing pure metals.
Experimental
Materials and research equipment.—The processing of used
catalysts was comprised of two distinct stages: the pyrometallurgical
Ni Al P Mn Pd Pt Rh
0.24 0.35 1.56 0.41 0.51 0.48 0.07
 Journal of The Electrochemical Society, 2024 171 012506
Table II. ICP-OES analysis results (in %) of Fe-PGM before oxidative leaching.
Composition % Fe Cr Cu Si
Fe-PGM alloy 67.56 7.41 0.37 12.49
Figure 3. The results of oxidative leaching of selected elements of the Fe-
PGM alloy in 20% H2SO4 + 30% H2O2.
stage and the chemical leaching or electrodeposition stage. Ground
automotive catalysts on a ceramic support were used as the input
material for pyrometallurgical tests. This material was obtained from
the European market. At each stage, the sample was analyzed using
ICP-OES - Inductively Coupled Plasma Optical Emission
Spectrometry 5800 Agilent or XRF X-ray fluorescence spectroscopy
Thermo Scientific, ARL Perform’X. The chemical composition
analysis of the input material for chemical leaching experiments
was conducted using ICP-OES due to the material being finely
ground for this process. However, the material used for the
electrochemical experiments was in the form of an anode, that was
prepared in a pyrometallurgical stage and directly cast into this form.
Therefore, it was not feasible to analyze it using ICP-OES for
homogenous composition, hence surface analyses from a larger
surface were prepared using XRF in this case.
Materials.—The spent auto catalyst was sourced from the EU
market and was comprised of ground car catalysts with a high
content of Silicon Carbide (SiC). The process temperature ranged
from 1500 °C–1600 °C and lasted 1–1.5 h from the moment the
suspected temperature was reached. The tests were conducted in a
reducing atmosphere without the addition of a reducer, as the SiC
present in the catalysts played this role. The collector metal was
Fe3O4, and the fluxes analyzed included Calcium Carbonate
(CaCO3), Calcium Oxide (CaO), and Sodium Tetraborate (Borax).
The pyrometallurgical stage involved the concentration of
Platinum Group Metals (PGMs) through reduction remelting of
catalysts with iron oxide (Fe3O4) and the addition of fluxes in a high-
temperature furnace. The furnace was capable of reaching tempera-
tures up to 1700 °C, allowing for the separation of the alloy (Fe-
PGMs) from the slag, which contained the metallic components of
Table III. XRF analysis results (in %) of Fe-PGM alloy obtained in pyrometallurgical stage.
Composition % Fe Cr Cu Si
Fe-PGM alloy 71.50 7.96 0.40 14.14
Ni Al P Mn Pd Pt Rh
0.29 0.03 1.58 0.37 0.62 0.61 0.08
the catalysts. The prepared Fe-PGM alloy served as the input
material used in subsequent stages.
The chemical leaching processes were realized according to the
following procedures:
• Reductive leaching using 20% H2SO4, S:L ratio of 1:6, at a
temperature of 80 °C, time 6 h. The finely crushed alloy, reduced to
below 100 μm grain size, was placed in a 5 l reactor capable of
maintaining the desired temperature and vigorously stirred. After the
stage completion, the solution was preliminarily separated using a
centrifuge, then filtered using a vacuum pump. The precipitate was
washed. Samples were taken of the initial alloy, at hourly intervals,
and of the final solid part, filtrate, and washings.
• Oxidative leaching using 20% H2SO4, S:L ratio of 1:5, with
the addition H2O2, at a temperature of 60 °C, time 6 h. The finely
crushed alloy, reduced to below 100 μm grain size, was placed in a
5 l reactor capable of maintaining the desired temperature and
vigorously stirred. Periodically, H2O2 was added during the process
to create oxidizing conditions. After the stage completion, the
solution was preliminarily separated using a centrifuge, then filtered
using a vacuum pump. The precipitate was washed. Samples were
taken of the initial alloy, at hourly intervals, and of the final solid
part, filtrate, and washings.
The electrochemical dealloying (ED) stage involved the dis-
solution of the alloy, followed by the selective precipitation of the
PGMs on the cathode with production of small amount of the anode
slime. The process has been carried out in an electrochemical tests
vessel of a 100 ml volume, there was an auxiliary/reference
electrode/cathode made of a stainless steel sheet with an area of
about 4 cm2 or a graphite rod with a surface area of about 2 cm2 and
an indicator electrode (anode) in the form of a Fe-PGM alloy
obtained according to the procedure described above and with a
surface area of about 1 cm2 and a thickness of more than 1 mm.
Exemplary anode sample made of Fe-PGM alloy that contain high
amount of silicon (Si) was presented on Fig. 1.
The electrochemical tests vessel was filled with the electrolytes
of the following compositions for different measurement series:
−1.25M FeSO4 ;
−0.5M H2 SO4 ;
−H2 SO4 0.5M + 0.1M NaCl;
−H2 SO4 0.5M + 2.0M NaCl;
−H2 SO4 0.5M + 4.0M NaCl;
The electrodes are connected using BNC connector to a
measuring device—a commercially available galvanostat/potentio-
stat Autolab: Metrohm VIONIC (powered by INTELLO-softwear)
enabling programmable electrolysis process. During electrolysis,
Ni Al P Mn Pd Pt Rh
0.25 1.31 2.09 0.53 0.61 0.53 0.08
 Journal of The Electrochemical Society, 2024 171 012506
Figure 4. Current vs potential graphs for anodic dissolution of Fe-PGM
alloy in 0.5 M H2SO4: (a) 2400 cycles of 1.3 V–1.6 V–1.3 V; (b) 4800 cycles
of 1.6 V–1.75 V–1.6 V.
current variation is measured as a function of time and potential. The
value of the recorded current is related to changes in the concentra-
tion of electroactive ions in the solution and to the value of the
potential at a given time and its rate of (linear) change in the
potentiodynamic process. The best results were obtained using
potentiodynamic process with the following electrolysis parameters:
temperature: 50 °C, potential change: from 1.6 V to 1.75 V and again
to 1.6 V, potential change rate: 100 mV s−1, electrolysis time over
1 h and anode working surface area about 1 cm2. After electro-
chemical anodic dissolution and cathodic deposition, the anode and
cathode deposit composition were investigated using the SEM/EDS
method. It should be noted that SEM/EDS test shows the surface
composition of the anode and cathode precipitate. The composition
of the electrolyte was tested before and after electrolysis by the ICP-
OES method using ICP OES 5800 Agilent apparatus. The most
important process parameters were determined on the basis of the
measurements of the following parameters: anode and cathode mass
before and after the process, the current and electric charge that was
Table IV. ICP-OES analysis results (in ppm) of sulfuric acid and solutions obtained by cyclic the potential of the cell filled with 0.5 M H2SO4
solution and Fe-PGM alloy anode that contain high amount of silicon (Si) and stainless steel cathode with potential sweep rate 100 mV s−1 at
temperature 25 °C.
Cr Cu Fe Mn
a) a) a) a)
H2SO4
1.3 V–1.6 V–1.3 V 137 1 520 6 17
1.6 V–1.75 V–1.6 V 407 4 1453 15
a) below detection limit of ICP-OES.
consumed in the process of potentiostatic or potentiodynamic
dissolution of the anode Fe-PGM alloy.
Results and Discussion
Chemical leaching.—The aim of the above stage was to remove
non-ferrous metals such as iron, chromium, and nickel through a
reductive leaching process. Additionally, to eliminate copper and
undissolved metals from the previous stage, oxidative leaching from
the Fe-PGM alloy was used, resulting in obtaining a concentrated
precipitate containing PGM intended for later separation of indivi-
dual platinum group metals. Unfortunately, the feedstock for the
chemical leaching stage was obtained from the smelting of spent
automotive catalysts with a high SiC content, ultimately containing a
high level of silicon. This alloy falls under the category of high
silicon materials, classified as having a silicon content above 14.5%,
consequently providing excellent corrosion resistance to H2SO4.
These materials display good resistance in oxidizing and reducing
environments and are not appreciably affected by concentration or
temperature.8–10 The composition of the Fe-PGM alloy used in
chemical leaching tests is presented in the Table I.
The results of reductive leaching of selected elements of the Fe-
PGM alloy were presented in Fig. 2. The efficiency of leaching for
selected elements exposed to 20% H2SO4 is depicted in the Fig. 2,
omitting metals that do not dissolve under such conditions. As can
be observed in Fig. 2, the presence of silicon in the alloy
significantly hinders the dissolution of metals that should be
susceptible to sulfuric acid action.
Additionally, the filtration of the obtained solution from the
precipitate resulting from dissolving the Fe-PGM alloy in H2SO4,
rich in silicon, poses a challenge due to this high silicon content.
Silicon induces gel formation or the precipitation of gelatinous
particles (separating from the solution due to the condensation of
polysilicic acids), significantly hindering the filtration process. Its
presence promotes the formation of fine-structured precipitates,
leading to the clogging of filter pores, requiring frequent cleaning
or filter replacement—hence the necessity for preliminary separation
using a centrifuge in this case. Furthermore, the high viscosity of the
solution, caused by silicon, further deteriorates the efficiency of the
filtration process and increases the time and difficulty of its
completion.
Furthermore, the dissolution of the analyzed Fe-PGM alloy in
H2SO4 is also hindered by its high chromium content. Chromium,
akin to silicon, enhances the alloy’s corrosion resistance. Moreover,
the intricate nature of the reaction between chromium and H2SO4
can lead to the formation of a stable passive layer on the alloy’s
surface, impeding the dissolution process and potentially requiring
additional chemical agents or processes to achieve the intended
effect.
Similarly to the reductive leaching, attempts at oxidative leaching
were then conducted (description above). The chemical composition
of the feedstock material for this stage is presented in Table II, while
the results of these experiments are shown in Fig. 3.
As seen in Fig. 3, the dissolution of Fe-PGM alloy containing a
significant amount of silicon hampers the dissolution of metals
within it, even though oxidative leaching. Similar to the case of
Ni P Si Pd Pt Rh Charge/C
Time/h
a) a) a) a) a) a)
a) a) a)
6 28 308/4 h
25 27 101 0.66 0.56 0.25 1476/4 h
 Journal of The Electrochemical Society, 2024 171 012506

Figure 5. Exemplary SEM image (a) and EDS spectrum (b) of the stainless steel cathode used in the process of electrochemical dealloying at
1.6 V–1.75 V–1.6 V of Fe-PGM.

Table V. ICP-OES analysis results (in ppm) of solutions obtained by (linear) cyclic the potential of the cell filled with 0.5 M H2SO4 solution with
different additions of NaCl for Fe-PGM alloy anode that contain high amount of silicon (Si) and graphite cathode with potential sweep rate
100 mV s−1 at temperature of 50 °C.

Cr Cu Fe Mn Ni P Si Pd Pt Rh Charge/C

H2SO4 0.5 M + ppm Time/h

0.1 M NaCl/1.6–1.75 V 762 7 3540 20 14 32 178 3 5 1 2472/3 h
2 M NaCl/1.6–1.75 V 994 20 5215 31 20 63 272 30 27 4 5833/3 h
2 M NaCl/1.6–1.75 V 1195 34 6239 39 25 88 266 27 23 4 7514/5 h
4 M NaCl/1.6–1.75 V 603 26 5132 26 29 43 127 32 31 4 4318/1.5 h
4 M NaCl/1.4–1.5 V 425 13 2595 15 10 33 124 17 31 2 2977/3 h

Figure 6. SEM image (a) and EDS spectrum (b) of the graphite rode cathode used in the process of electrochemical dealloying of Fe-PGM alloy in the solutions
of H2SO4 with different concentrations of NaCl.

In the analyzed scenario, due to unsatisfactory outcomes in

Table VI. Results of EDS analysis of graphite rod cathode.
Element SEM/EDS analysis [wt%]
C 95.2–96.1
O 3.4–4.4
Si 0.1–0.2
S 0.2–0.3
reductive leaching, silicon forms sparingly soluble compounds,
leading to the formation of precipitates or gels, which in turn
complicates the process of dissolving the metals present in the alloy.
dissolving the Fe-PGM alloy via reductive and oxidative leaching,
an additional step of preliminary silicon removal can be incorporated
into the process. According to the publication,11 NaOH at elevated
temperatures can be used to remove silicon from the alloy. The
reaction with strong bases can lead to the formation of soluble
silicate complexes, enabling the extraction of silicon from the solid
phase. Elevated temperatures can accelerate the reaction rate,
expediting the silicon removal process. Incorporating an additional
stage of silicon removal using hot, concentrated NaOH before the
dissolution process of Fe-PGM alloy in sulfuric acid may involve
several organizational and environmental challenges. From an
organizational standpoint, adding another stage to the process can
complicate logistics and overall process control. This requires
 Journal of The Electrochemical Society, 2024 171 012506

Figure 7. SEM images (a, c, e) and EDS spectra (b, d, f) of the graphite rod cathode after it is used in the process of electrochemical dealloying at
1.6 V–1.75 V–1.6 V of Fe-PGM in the solution of 0.5 M H2SO4 with 2 M NaCl, electrolysis time 5 h.

additional equipment, procedural monitoring, and time management,

Table VII. EDS analysis of the sample of the graphite rod cathode
increasing the complexity of the operation. Additionally, aligning
after it is used in the process of electrochemical dealloying at safety protocols and chemical processing regulations may be time-
1.6 V–1.75 V–1.6 V of Fe-PGM in the solution of 0.5 M H2SO4 with consuming and demand extra resources. Environmentally, removing
2 M NaCl, electrolysis time 5 h. silicon using hot, concentrated NaOH might generate additional by-
products and chemical waste, necessitating proper waste manage-
SEM/EDS analysis [wt%] ment practices to avoid adverse environmental impacts. Moreover,
disposing of spent solutions might present challenges due to their
Element Range Avg. toxic or acidic nature, requiring specific disposal procedures to
prevent environmental contamination.
C 77.8–81.9 80.4 On the other hand, according to the literature reports12,13 and test
O 0–2.4 1.8 results (not covered in the our publication), the dissolution of Fe-
Si 0–0.6 0.2 PGM alloy with lower silicon content does not present difficulties.
Cl 0.8–1.0 0.9 However, for the analyzed material, due to the initial composition
Cu 1.4 1.4 of used automotive catalysts (an increasing market share of catalysts
Pd 3.2–4.4 3.8 with high SiC content), high amounts of Si contribute to inadequate
Pt 10.1–14.3 11.7 chemical leaching efficiency of non-ferrous metals and copper. For
 Journal of The Electrochemical Society, 2024 171 012506
this material, the ideal approach involves using electrodeposition
combined with electrochemical dealloying.
Electrochemical Leaching/Dealloying (ED) and
Electrodeposition
According to literature data5 Fe-PGMs alloy obtained in the iron-
capturing recycling process can be electrochemically dissolved in
the aqueous solution of FeSO4 in the following conditions: potential
(0.5–0.8 V), concentration of Fe2+ (1.0–1.5 mol L−1), temperature
(60 °C–80 °C), pH (3.0–3.5). It has been reported that after such
potentiostatic electrolysis at 0.7 V, PGMs were separated from the
iron matrix and enriched in the anode slime (85%–90%) and pure
iron was deposited on the cathode. In our studies Fe-PGM alloy that
contain high amount of silicon (Si) has been used as the anode
material for the potentiostatic electrolysis at potentials ranging from
0.7 V to 1.3 V in 1.25 M aqueous solution of FeSO4 at 55 °C–60 °C
and there was no anodic dissolution of the alloy. The only process
observed in such conditions is water electrolysis. Consequently, very
high corrosion resistance of the Fe-PGM alloy that contain high
amount of silicon (Si) discussed above has been confirmed in the
electrochemical process, too. The composition of the Fe-PGM alloy
used in electrochemical leaching/dealloying and deposition tests is
presented in the Table III.
The results of the electrochemical dealloying in 0.5 M H2SO4 are
presented below (Fig. 4). In the Table IV the results of the
electrochemical dealloying for two different ranges of the potential
are presented. This example shows very well the advantages of
electrochemical dealloying process, where potential is used to
control the selectivity and rate of the process instead of chemical
reagents additions or temperature raise in the traditional leaching
process. At lower potentials range the rate of the process is lower,
which is clear from the lower charge (current) consumed in the
process as well as much lower concentrations of the elements
transferred to the electrolyte in the process. On the other hand,
selectivity of the process is controlled uniquely by the electroche-
mical parameters such as potential range, because at lower potentials
PGMs are not dissolved to the solution from the alloy. At higher
potentials detectable concentrations of Pd, Pt and Rh have been
dissolved in the ED process. Apart from the main anode process,
which is dissolution of the alloy components to the solution there is
oxygen evolution reaction (OER). At the cathode the main process is
the reduction of the metal ions and hydrogen evolution reaction
(HER) is a parallel (parasitic) process. In Figs. 4–5 changes of the
current and potential are presented for both processes presented in
the Table IV. Results of EDS analysis of the cathode surface after
electrolysis confirm the anodic dissolution of PGMs, because apart
from the lines of stainless steel base, the lines of approximately
1 wt% of Cu and approximately 0.8 wt% of Pd electrodeposited
from the solution are registered.
Exemplary SEM image and EDS for the analyzed cases are
presented in the Fig. 5. EDS spectra show the lines of the stainless
steel base as well as lines of approximately 1 wt% of Cu and
approximately 0.8 wt% of Pd electrodeposited from the solution.
The above described experiments with the usage of sulfuric acid
solution show the feasibility of electrochemical dealloying of Fe PGM
alloy anode that contain high amount of silicon (Si). ED process is
combined with selective electrodeposition of the alloy components at
the cathode. Below are presented the results in the ED process
conditions, which can be exploited in the scalable applications,
because much higher rates of the anodic dissolution and cathodic
deposition are obtained. The increase in the anodic dissolution is
achieved by addition of complexing agent, which in the case of
current study is chloride anion.14 Instead of the stainless steel a
graphite rod is used as the cathode material to enable simple recovery
of the deposited valuable metals from the cathode. From the results
presented in the Table V, it can be concluded that the increase of the
Figure 8. Current vs potential for anodic dissolution of Fe-PGM alloy in
0.5 M H2SO4 with 2 M NaCl.
Table VIII. EDS analysis of the graphite cathode after it is used in
the process of electrochemical dealloying at 1.6 V–1.75 V–1.6 V of
Fe-PGM in the solution of 0.5 M H2SO4 with 0.1 M NaCl, electrolysis
time 3 h.
Element SEM/EDS analysis [wt%]
C 67.2–71.0
O 8.6–10.8
Na 0.5–0.8
Si <−0.4
S 2.0–2.7
Cl 0.4–0.5
Fe 0.4–0.5
Cu 3.7–3.8
Pd 3.6–3.9
Pt 9.4–10.6
NaCl addition from 0.1 M to 4 M to 0.5 M H2SO4 solution increases
the rate of the Fe-PGM anode dealloying. For instance the same
concentrations of PGMs and less noble metals like e.g. Fe can be
obtained in the electrolyte in approximately half of the electrolysis
time when 4 M of NaCl addition is used instead of 2 M NaCl. Using
low NaCl concentrations e.g. 0.1 M may lead to the selective anodic
dissolution of most alloy components except of PGMs. This phenom-
enon can be used in the design of the selective ED process indeed. The
process enable separation of Pt and Pd from Rh, which remains in the
anodic slime and/or in the solution. On the other hand, even at high
concentrations of NaCl equal to 4 M, potential can be used to
influence the relative rate of different metals dissolution like in the
case of Pt and Pd presented in the Table V. It should be noticed that
cathode product is reach in Pt and Pd with Cu as the main impurity,
which can be easily separated from PGMs in the next stage of the
cathode product treatment. SEM image and EDS spectrum of the
graphite rode cathode used in the process of electrochemical deal-
loying of Fe-PGM alloy in the solutions of H2SO4 with different
concentrations of NaCl are presented in the Fig. 6.
Results of EDS analysis of graphite rod cathode is presented in
the Table VI. SEM images and EDS spectra of the graphite rod
cathode after it is used in the process of electrochemical dealloying
at 1.6 V–1.75 V–1.6 V of Fe-PGM in the solution of 0.5 M H2SO4
with 2 M NaCl, electrolysis time 5 h (Fig. 7) and Table VII show the
lines of the graphite cathode base as well as lines of approximately
 Journal of The Electrochemical Society, 2024 171 012506

Figure 9. SEM images (a, c, e) and EDS spectra (b, d, f) of the graphite rod cathode after it is used in the process of electrochemical dealloying at
1.6 V–1.75 V–1.6 V of Fe-PGM in the solution of 0.5 M H2SO4 with 0.1 M NaCl, electrolysis time 3 h.

1 wt% of Cu. Approximately 3.8 wt% of Pd and approximately 12%
of Pt electrodeposited from the solution. Comparison of current vs
potential for anodic dissolution of Fe-PGM alloy in 0.5 M H2SO4
with 2 M NaCl described in the Table VII: 5950 cycles of
1.6 V–1.75 V–1.6 V is presented on Fig. 8.
EDS analysis (Table VIII) of the sample from the Fig. 9 show the
lines of the graphite cathode base as well as lines of approximately
3.8 wt% of Cu. Approximately 3.8 wt% of Pd and approximately
10% of Pt electrodeposited from the solution. Comparison of current
vs potential for anodic dissolution of Fe-PGM alloy in 0.5 M H2SO4
with 0.1 M NaCl is shown in the Fig. 10.
Based on the obtained feasibility studies results the following
estimates of the ED parameters process for Fe-PGM alloy anode that
contain high amount of silicon (Si) and using the electrolyte of 0.5 M
H2SO4 with 4 M NaCl, graphite cathode with potential sweep rate
100 mV s−1 for potential change 1.6 V-1.75 V-1.6 V at temperature
of 50 °C are established:
1. rate of the alloy dissolution 3.8 kg per 1 h and per 1 m2 of the
anode surface area,
2. rate of the Pd+Pt dissolution 87 g per 1 h and per 1 m2 of the
anode surface area,
3. energy consumption for the Fe-PGM alloy dissolution approxi-
mately 3.5 kWh kg−1.
The above discussion and estimated parameters of the ED process
for Fe-PGM alloy anode that contain high amount of silicon (Si) show
that that the process is feasible and potentially scalable with very good
economic effectiveness and relatively low environmental footprint.
A material containing Pt and Pd, obtained through electrodeposi-
tion, can find applications across various industrial domains. Most
commonly, owing to their catalytic properties, they can be utilized in
the production of fuel cells (Pt and Pd-containing catalyst structures
for silicon-based formic acid micro fuel cells15), catalytic conver-
sion, or electrochemical oxygen reduction. Additionally, their high
 Journal of The Electrochemical Society, 2024 171 012506
Figure 10. Current vs potential for anodic dissolution of Fe-PGM alloy in
0.5 M H2SO4 with 0.1 M NaCl described in the Table VIII: 3550 cycles of
1.6 V–1.75 V–1.6 V.
corrosion resistance renders them valuable in the electronics industry
and in the production of high-quality jewelry.
Conclusions
In the present article a new and innovative approach for the selective
separation of platinum group metals (Pt, Pd, Rh) from Fe-PGM alloys
that contain high amounts of silicon (Si) is discussed. The challenge
with processing these alloys by conventional hydrometallurgical
methods is that the high content of silicon makes the alloy almost
completely resistant to corrosion and leaching in acids. Consequently,
our experimental results of chemical leaching show that due to the
initial composition of used automotive catalysts (an increasing market
share of catalysts with high SiC content), high amounts of Si contribute
to inadequate chemical leaching efficiency of non-ferrous metals and
copper. For this material, the ideal approach involves using electro-
deposition combined with electrochemical dealloying.
The results of the feasibility study outlined in this paper offer
valuable insights into the parameters governing the electrodeposition
(ED) process of anodes composed of the Fe-PGM alloy, enriched
with a high silicon content. Using a 0.5 M H2SO4 electrolyte
combined with 4 M NaCl, employing a graphite cathode and specific
potential sweep rates between 1.6 V–1.75 V–1.6 V at a controlled
temperature of 50 °C, significant estimates have been established.
The results indicate a dissolution rate of 3.8 kg per hour per 1 m2
of anode surface area for the alloy, alongside a dissolution rate of
87 g per hour per 1 m2 of anode surface area specifically for Pd+Pt.
These findings underscore the viability and efficiency of the ED
process parameters in managing Fe-PGM alloy anodes, particularly
those with elevated silicon content. Such insights serve as a
foundational basis for further optimization and development within
this domain, potentially contributing to enhanced industrial applica-
tions and resource management within the field.
The above discussion and estimated parameters of the ED
process for Fe-PGM alloy anode that contain high amount of silicon
(Si) show that that the process is feasible and potentially scalable
with very good economic effectiveness and relatively low environ-
mental footprint. The advantage of electrochemical dealloying
process, where potential range and rate of the (linear) potential
change is used to control the selectivity and rate of the process
instead of chemical reagents additions or temperature and/or
pressure raise in the traditional leaching processes.
It should also be emphasized that the conditions presented for
conducting the process are those specified in our feasibility studies.
However, altering the solution composition and other conditions of
the ED process can influence the mechanism and kinetics of the
electrochemical deposition process. Consequently, modifying the
ED process conditions can result in the dissolution of different
metals, which is an advantage of electrochemical leaching.
Acknowledgments
Elemental Strategic Metals Sp. z o. o. is implementing the
project: “Research, development and the first industrial implementa-
tion of innovative technologies for recycling Li-ion batteries and
used catalysts with recovery of strategic metals,” including the
development of technologies for safe, environmentally friendly and
economical transport, storage and recycling of Li-ion batteries and
other waste containing strategic metals. The ESM project was co-
financed by the European Union in accordance with EC Decision C
(2019) 8823 of December 9, 2019 under recruitment No. 8/1.1.1/
2020 - Fast track - IPCEI organized by the National Center for
Research and Development.
ORCID
Przemysław Łoś https://orcid.org/0000-0001-8759-0266
Agnieszka Sobianowska-Turek https://orcid.org/0000-0003-2154-
8609
Michał Janosz https://orcid.org/0009-0001-9224-4605
Agnieszka Fornalczyk https://orcid.org/0000-0002-2149-1422
References
1. M. Saternus, A. Fornalczyk, W. Gasior, A. Debski, and S. Terlicka, Catalysts, 10,
880 (2020).
2. G. Paryjczak, A. Lewicki, and M. Zaborski, Green Chem. (Polish Academy of
Sciences, Lodz) Vol. 3, p. 208 (2005).
3. I. Yakoumis, M. Panou, A. Moschovi, and D. Panias, Cleaner Engineering and
Technology, 3, 100112 (2021).
4. S. Anantharaj and S. Noda, Nano Energy, 114, 108624 (2023).
5. Q. Wen, Y. Ding, H. Zheng, and S. Zhang, J. Clean. Prod., 271, 122829 (2020).
6. M. Soszko, M. Łukaszewski, and A. Czerwinski, J. Electroanal. Chem., 877,
114547 (2020).
7. https://preciousmetalscommoditymanagement.com/blog/the-auto-catalyst-precious-
metals-dilemma# access 21.11.2023.
8. Ramesh Singh et al., “Cast iron and cast steel.” Applied Welding Engineering
(Third Edition), 2020 (Elsevier)(Elsevier) Vol. 3 (2020), access 19.01.2024.
9. R. V. Riley, Silicon iron-the acid resisting alloy, 124, JHMS26 (1992).
10. A. S. Kinsela et al., Environ. Sci. Technol., 50, 11663 (2016).
11. M. Fertani-Gmati and M. Jemal, Thermochim. Acta, 513, 43 (2011).
12. Y. Dinga, H. Zhenga, S. Zhanga, L. B. Bo Wua, and Z. Jianb, Resources,
Conservation & Recycling, 155, 104644 (2020).
13. F. K. Crundwell, M. S. Moats, V. Ramachandran, T. Robinson, and W. G. Davenport,
Extractive Metallurgy of Nickel, Cobalt and Platinum Group Metal (Elsevier,
Amsterdam) (2011).
14. C. Diac, F. Iuliana Maxim, R. Tirca, A. Ciocanea, F. Valeriu, E. Vasile, and
S. N. Stamatin, Metals, 10, 822 (2020).
15. R. S. Jayashree, J. S. Spendelow, J. Yeom, C. Rastog, M. A. Shannon, and
P. J. A. Kenis, Electrochim. Acta, 50, 4674 (2005).