Jovićević, Jovan J.

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  • Jovićević, Jovan J. (3)
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Author's Bibliography

Electrochemical deposition of ruthenium oxide from deep eutectic solvent

Petrović, Nataša M.; Cvetković, Vesna. S; Jović, Vladimir D; Barudžija, Tanja; Jovićević, Jovan J.

(Serbian Chemical Society, 2024)

TY  - CONF
AU  - Petrović, Nataša M.
AU  - Cvetković, Vesna. S
AU  - Jović, Vladimir D
AU  - Barudžija, Tanja
AU  - Jovićević, Jovan J.
PY  - 2024
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/7651
AB  - Transition metal oxides (TMOs) have gathered increasing attention in material science due to their good electrical,
mechanical, optical properties and great chemical and thermal stability. Among them, ruthenium oxide (RuO2), with
its excellent catalytic performances has been the subject of numerous studies. It serves as a crucial material for
electrodes in (electro)catalysis, energy storage systems, and semiconductor devices. RuO2-based catalysts have
shown good potential in many important reactions such as the low-temperature dehydrogenation of small
molecules (NH3, HCl, methanol), and have been utilized in industrial electrolysis for chlorine-alkali production [1,2].
There are numerous techniques to synthesize RuO2 [1]. In response to the challenges associated with RuO2
synthesis, and to customize the particle size and shape of RuO2, an electrochemical deposition from a new class of
non-aqueous electrolytes, namely the deep eutectic solvents (DESs), can be a good alternative. So far, there have
been recorded some attempts to electrochemically deposit ruthenium/ruthenium oxides from DES [3,4].
This study focuses on the electrochemical deposition of ruthenium oxide onto palladium working electrode from
choline chloride (ChCl): urea (1:2 ratio) DES at 80 °C with 0.01M Ru(III) ions concentration. RuCl3 was added as a
source of Ru ions in the working electrolyte. To determine the potential range available for Ru electrodeposition in
DES, cyclic voltammetry (CV) on Pd working electrode in the electrolyte containing ChCl and urea was recorded.
The potential window of electrochemical stability was between -1.2 and +0.3V vs. Pt. The electrochemical behaviour
of Ru(III) in choline chloride-urea has been investigated at palladium using cyclic voltammetry (CV) and square wave
voltammetry (SWV). The CV results showed only cathodic peaks without corresponding anodic counterparts, and
SWV was used for further investigation in order to gain a better understanding of the Ru(III) electroreduction
process. The electrochemical impedance spectroscopy (EIS) results indicate diffusion-controlled RuO2 deposition.
Relatively small deposition overpotential (-1.0 V) applied in the electrodeposition experiments, resulted in
ruthenium oxide being electrodeposited. The morphology of the obtained deposits was characterized using
scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). X-ray diffraction (XRD) analysis of
the produced particles provided conformation that the RuO2 was formed onto a palladium working substrate.
PB  - Serbian Chemical Society
C3  - 9th Regional Symposium on Electrochemistry - South-East Europe, Book of Abstract, 3 to 7 June, 2024, Novi Sad, Serbia
T1  - Electrochemical deposition of ruthenium oxide from deep eutectic solvent
SP  - 98
EP  - 98
DO  - 10.5281/zenodo.11194247
ER  - 
@conference{
author = "Petrović, Nataša M. and Cvetković, Vesna. S and Jović, Vladimir D and Barudžija, Tanja and Jovićević, Jovan J.",
year = "2024",
abstract = "Transition metal oxides (TMOs) have gathered increasing attention in material science due to their good electrical,
mechanical, optical properties and great chemical and thermal stability. Among them, ruthenium oxide (RuO2), with
its excellent catalytic performances has been the subject of numerous studies. It serves as a crucial material for
electrodes in (electro)catalysis, energy storage systems, and semiconductor devices. RuO2-based catalysts have
shown good potential in many important reactions such as the low-temperature dehydrogenation of small
molecules (NH3, HCl, methanol), and have been utilized in industrial electrolysis for chlorine-alkali production [1,2].
There are numerous techniques to synthesize RuO2 [1]. In response to the challenges associated with RuO2
synthesis, and to customize the particle size and shape of RuO2, an electrochemical deposition from a new class of
non-aqueous electrolytes, namely the deep eutectic solvents (DESs), can be a good alternative. So far, there have
been recorded some attempts to electrochemically deposit ruthenium/ruthenium oxides from DES [3,4].
This study focuses on the electrochemical deposition of ruthenium oxide onto palladium working electrode from
choline chloride (ChCl): urea (1:2 ratio) DES at 80 °C with 0.01M Ru(III) ions concentration. RuCl3 was added as a
source of Ru ions in the working electrolyte. To determine the potential range available for Ru electrodeposition in
DES, cyclic voltammetry (CV) on Pd working electrode in the electrolyte containing ChCl and urea was recorded.
The potential window of electrochemical stability was between -1.2 and +0.3V vs. Pt. The electrochemical behaviour
of Ru(III) in choline chloride-urea has been investigated at palladium using cyclic voltammetry (CV) and square wave
voltammetry (SWV). The CV results showed only cathodic peaks without corresponding anodic counterparts, and
SWV was used for further investigation in order to gain a better understanding of the Ru(III) electroreduction
process. The electrochemical impedance spectroscopy (EIS) results indicate diffusion-controlled RuO2 deposition.
Relatively small deposition overpotential (-1.0 V) applied in the electrodeposition experiments, resulted in
ruthenium oxide being electrodeposited. The morphology of the obtained deposits was characterized using
scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). X-ray diffraction (XRD) analysis of
the produced particles provided conformation that the RuO2 was formed onto a palladium working substrate.",
publisher = "Serbian Chemical Society",
journal = "9th Regional Symposium on Electrochemistry - South-East Europe, Book of Abstract, 3 to 7 June, 2024, Novi Sad, Serbia",
title = "Electrochemical deposition of ruthenium oxide from deep eutectic solvent",
pages = "98-98",
doi = "10.5281/zenodo.11194247"
}
Petrović, N. M., Cvetković, Vesna. S., Jović, V. D., Barudžija, T.,& Jovićević, J. J.. (2024). Electrochemical deposition of ruthenium oxide from deep eutectic solvent. in 9th Regional Symposium on Electrochemistry - South-East Europe, Book of Abstract, 3 to 7 June, 2024, Novi Sad, Serbia
Serbian Chemical Society., 98-98.
https://doi.org/10.5281/zenodo.11194247
Petrović NM, Cvetković VS, Jović VD, Barudžija T, Jovićević JJ. Electrochemical deposition of ruthenium oxide from deep eutectic solvent. in 9th Regional Symposium on Electrochemistry - South-East Europe, Book of Abstract, 3 to 7 June, 2024, Novi Sad, Serbia. 2024;:98-98.
doi:10.5281/zenodo.11194247 .
Petrović, Nataša M., Cvetković, Vesna. S, Jović, Vladimir D, Barudžija, Tanja, Jovićević, Jovan J., "Electrochemical deposition of ruthenium oxide from deep eutectic solvent" in 9th Regional Symposium on Electrochemistry - South-East Europe, Book of Abstract, 3 to 7 June, 2024, Novi Sad, Serbia (2024):98-98,
https://doi.org/10.5281/zenodo.11194247 . .

Off-gases emission during the rare earth electrolysis from magnet recycling derived oxides

Petrović, Nataša M.; Cvetković, Vesna. S; Prasakti, Laras; Feldhaus, Dominic; Friedrich, Bernd; Jovićević, Jovan J.; Petrović, Nataša

(Serbian Chemical Society, 2024)

TY  - CONF
AU  - Petrović, Nataša M.
AU  - Cvetković, Vesna. S
AU  - Prasakti, Laras
AU  - Feldhaus, Dominic
AU  - Friedrich, Bernd
AU  - Jovićević, Jovan J.
AU  - Petrović, Nataša
PY  - 2024
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/7650
AB  - In the progressive energy transition process, rare earth elements (REE) became key components in crucial products
that play a central role in the development of renewable energy and low-carbon technologies. With China currently
producing more than 90 % of the world's REE output, many of the world's economies are facing REE supply risk [1].
To address this problem, many countries need to look for alternative resources of rare earths, e.g. recycling of these
elements from REE-containing end-of-life products. A new route for recovery of REE from NdFeB magnet scrap,
using a combination of pyrometallurgical treatment of spent NdFeB magnets, and a subsequent molten salt
electrolysis process, has been investigated in the authors’ laboratory [2]. The magnet recycling derived oxides
(MRDO), were produced from spent NdFeB magnets by oxidation in air and subsequent carbothermal reduction
under an 80 mbar Ar gas atmosphere. High-temperature molten salt electrolysis was introduced as an option that
enables the separation of rare earth elements from fluoride-based molten salts using produced MRDO [3]. One of
the challenges in this electrochemical approach for REE electrowinning is effective control of the anode effects to
make the electrolytic production of rare earths more environmentally friendly [3,4]. Minimizing the perfluorocarbon
compounds emission (PFC), in rare earth electrolysis, should be the primary goal, owing to their high global
warming potential [4,5].
In the present work, we investigated the off-gases emissions during the REE electrolysis from NdFeB magnet scrap
using in-situ FTIR-spectrometry, in order to understand the formation pathways of CO, CO2, and perfluorocarbon
gases (CF4 and C2F6) made at the anode. The electrolytic extraction of rare earths from fluoride-based molten salts
with different contents of MRDO present was performed using molybdenum (Mo) as a cathode, tungsten (W) as a
reference electrode, and a glassy carbon (GC) electrode as an anode. It was found that depending on the content
of the starting material, the dissolution of MRDO in their corresponding fluoride molten salts most probably induces
the formation of different oxyfluoride complexes and their subsequent reactions on the GC anode. The anode
reactions in the fluoride-based melts are, most likely, results of either oxide or fluoride formation by exchange with
the fluoride or oxide complexes present in the electrolyte. The produced oxygen subsequently reacts with carbon
to generate CO and CO2. With F− present, PFC compounds such as CF4 and C2F6 can also be formed from a GC anode.
The anode gas products are composed mainly of CO and CO2. The average CO2 concentration was approximately
450 ppm, while CO concentration was around 40 ppm. CF4 emissions in off-gas products were detected periodically,
except for some spikes, and even then, the concentration was below 4 ppm. C2F6 was not detected. The results
indicate that the electrodeposition of REE within the applied potential range occurs at the expense of their
corresponding oxides, provided by MRDO. To develop a more efficient RE recovery process, we opted for a low
deposition overpotential to suppress the emission of greenhouse gases and further enhance the control of their
emission in rare earth electrolysis.
PB  - Serbian Chemical Society
C3  - 9th Regional Symposium on Electrochemistry - South-East Europe, Book of Abstract, 3 to 7 June, 2024, Novi Sad, Serbia
T1  - Off-gases emission during the rare earth electrolysis from magnet recycling derived oxides
SP  - 123
EP  - 123
DO  - 10.5281/zenodo.11194247
ER  - 
@conference{
author = "Petrović, Nataša M. and Cvetković, Vesna. S and Prasakti, Laras and Feldhaus, Dominic and Friedrich, Bernd and Jovićević, Jovan J. and Petrović, Nataša",
year = "2024",
abstract = "In the progressive energy transition process, rare earth elements (REE) became key components in crucial products
that play a central role in the development of renewable energy and low-carbon technologies. With China currently
producing more than 90 % of the world's REE output, many of the world's economies are facing REE supply risk [1].
To address this problem, many countries need to look for alternative resources of rare earths, e.g. recycling of these
elements from REE-containing end-of-life products. A new route for recovery of REE from NdFeB magnet scrap,
using a combination of pyrometallurgical treatment of spent NdFeB magnets, and a subsequent molten salt
electrolysis process, has been investigated in the authors’ laboratory [2]. The magnet recycling derived oxides
(MRDO), were produced from spent NdFeB magnets by oxidation in air and subsequent carbothermal reduction
under an 80 mbar Ar gas atmosphere. High-temperature molten salt electrolysis was introduced as an option that
enables the separation of rare earth elements from fluoride-based molten salts using produced MRDO [3]. One of
the challenges in this electrochemical approach for REE electrowinning is effective control of the anode effects to
make the electrolytic production of rare earths more environmentally friendly [3,4]. Minimizing the perfluorocarbon
compounds emission (PFC), in rare earth electrolysis, should be the primary goal, owing to their high global
warming potential [4,5].
In the present work, we investigated the off-gases emissions during the REE electrolysis from NdFeB magnet scrap
using in-situ FTIR-spectrometry, in order to understand the formation pathways of CO, CO2, and perfluorocarbon
gases (CF4 and C2F6) made at the anode. The electrolytic extraction of rare earths from fluoride-based molten salts
with different contents of MRDO present was performed using molybdenum (Mo) as a cathode, tungsten (W) as a
reference electrode, and a glassy carbon (GC) electrode as an anode. It was found that depending on the content
of the starting material, the dissolution of MRDO in their corresponding fluoride molten salts most probably induces
the formation of different oxyfluoride complexes and their subsequent reactions on the GC anode. The anode
reactions in the fluoride-based melts are, most likely, results of either oxide or fluoride formation by exchange with
the fluoride or oxide complexes present in the electrolyte. The produced oxygen subsequently reacts with carbon
to generate CO and CO2. With F− present, PFC compounds such as CF4 and C2F6 can also be formed from a GC anode.
The anode gas products are composed mainly of CO and CO2. The average CO2 concentration was approximately
450 ppm, while CO concentration was around 40 ppm. CF4 emissions in off-gas products were detected periodically,
except for some spikes, and even then, the concentration was below 4 ppm. C2F6 was not detected. The results
indicate that the electrodeposition of REE within the applied potential range occurs at the expense of their
corresponding oxides, provided by MRDO. To develop a more efficient RE recovery process, we opted for a low
deposition overpotential to suppress the emission of greenhouse gases and further enhance the control of their
emission in rare earth electrolysis.",
publisher = "Serbian Chemical Society",
journal = "9th Regional Symposium on Electrochemistry - South-East Europe, Book of Abstract, 3 to 7 June, 2024, Novi Sad, Serbia",
title = "Off-gases emission during the rare earth electrolysis from magnet recycling derived oxides",
pages = "123-123",
doi = "10.5281/zenodo.11194247"
}
Petrović, N. M., Cvetković, Vesna. S., Prasakti, L., Feldhaus, D., Friedrich, B., Jovićević, J. J.,& Petrović, N.. (2024). Off-gases emission during the rare earth electrolysis from magnet recycling derived oxides. in 9th Regional Symposium on Electrochemistry - South-East Europe, Book of Abstract, 3 to 7 June, 2024, Novi Sad, Serbia
Serbian Chemical Society., 123-123.
https://doi.org/10.5281/zenodo.11194247
Petrović NM, Cvetković VS, Prasakti L, Feldhaus D, Friedrich B, Jovićević JJ, Petrović N. Off-gases emission during the rare earth electrolysis from magnet recycling derived oxides. in 9th Regional Symposium on Electrochemistry - South-East Europe, Book of Abstract, 3 to 7 June, 2024, Novi Sad, Serbia. 2024;:123-123.
doi:10.5281/zenodo.11194247 .
Petrović, Nataša M., Cvetković, Vesna. S, Prasakti, Laras, Feldhaus, Dominic, Friedrich, Bernd, Jovićević, Jovan J., Petrović, Nataša, "Off-gases emission during the rare earth electrolysis from magnet recycling derived oxides" in 9th Regional Symposium on Electrochemistry - South-East Europe, Book of Abstract, 3 to 7 June, 2024, Novi Sad, Serbia (2024):123-123,
https://doi.org/10.5281/zenodo.11194247 . .

Study of Nd deposition onto W and Mo Cathodes from Molten Oxide-Fluoride Electrolyte

Cvetković, Vesna S.; Vukićević, Nataša; Feldhaus, Dominic; Barudžija, Tanja; Stevanović, Jasmina; Friedrich, Bernd; Jovićević, Jovan J.

(Electrochemical Science Group (ESG), 2020)

TY  - JOUR
AU  - Cvetković, Vesna S.
AU  - Vukićević, Nataša
AU  - Feldhaus, Dominic
AU  - Barudžija, Tanja
AU  - Stevanović, Jasmina
AU  - Friedrich, Bernd
AU  - Jovićević, Jovan J.
PY  - 2020
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/3708
AB  - Electrochemical reduction processes of Nd(III) on tungsten and molybdenum electrodes in NdF3+LiF and NdF3+LiF+Nd2O3 were investigated by cyclic voltammetry, chronoamperometry and open circuit measurements. Electrolytes and electrodes were examined after neodymium electrodeposition by optical microscopy and XRD. It was found that tungsten and molybdenum working electrodes behave identically during neodymium complexed ion reduction processes. Their reversible potentials in the electrolytes used differed only by 10 mV, and so did the potentials of the neodymium ion reduction processes. The recorded results indicated that the Nd(III) ions in the melts were reduced in two steps: Nd(III) → Nd(II) and Nd(II) → Nd(0). These consecutive processes are predominantly mass transfer controlled. Electrolytically obtained metal appeared to accumulate on the cathode and no metal neodymium was recorded in the solidified electrolyte placed close to the cathode after completed electrodeposition process. However, it was found that NdF2 formed by the disproportionation reaction between Nd(III) and that deposited Nd(0) coexists with other complex components in the electrolytes used.
PB  - Electrochemical Science Group (ESG)
T2  - International Journal of Electrochemical Science
T1  - Study of Nd deposition onto W and Mo Cathodes from Molten Oxide-Fluoride Electrolyte
VL  - 15
IS  - 7
SP  - 7039
EP  - 7052
DO  - 10.20964/2020.07.82
ER  - 
@article{
author = "Cvetković, Vesna S. and Vukićević, Nataša and Feldhaus, Dominic and Barudžija, Tanja and Stevanović, Jasmina and Friedrich, Bernd and Jovićević, Jovan J.",
year = "2020",
abstract = "Electrochemical reduction processes of Nd(III) on tungsten and molybdenum electrodes in NdF3+LiF and NdF3+LiF+Nd2O3 were investigated by cyclic voltammetry, chronoamperometry and open circuit measurements. Electrolytes and electrodes were examined after neodymium electrodeposition by optical microscopy and XRD. It was found that tungsten and molybdenum working electrodes behave identically during neodymium complexed ion reduction processes. Their reversible potentials in the electrolytes used differed only by 10 mV, and so did the potentials of the neodymium ion reduction processes. The recorded results indicated that the Nd(III) ions in the melts were reduced in two steps: Nd(III) → Nd(II) and Nd(II) → Nd(0). These consecutive processes are predominantly mass transfer controlled. Electrolytically obtained metal appeared to accumulate on the cathode and no metal neodymium was recorded in the solidified electrolyte placed close to the cathode after completed electrodeposition process. However, it was found that NdF2 formed by the disproportionation reaction between Nd(III) and that deposited Nd(0) coexists with other complex components in the electrolytes used.",
publisher = "Electrochemical Science Group (ESG)",
journal = "International Journal of Electrochemical Science",
title = "Study of Nd deposition onto W and Mo Cathodes from Molten Oxide-Fluoride Electrolyte",
volume = "15",
number = "7",
pages = "7039-7052",
doi = "10.20964/2020.07.82"
}
Cvetković, V. S., Vukićević, N., Feldhaus, D., Barudžija, T., Stevanović, J., Friedrich, B.,& Jovićević, J. J.. (2020). Study of Nd deposition onto W and Mo Cathodes from Molten Oxide-Fluoride Electrolyte. in International Journal of Electrochemical Science
Electrochemical Science Group (ESG)., 15(7), 7039-7052.
https://doi.org/10.20964/2020.07.82
Cvetković VS, Vukićević N, Feldhaus D, Barudžija T, Stevanović J, Friedrich B, Jovićević JJ. Study of Nd deposition onto W and Mo Cathodes from Molten Oxide-Fluoride Electrolyte. in International Journal of Electrochemical Science. 2020;15(7):7039-7052.
doi:10.20964/2020.07.82 .
Cvetković, Vesna S., Vukićević, Nataša, Feldhaus, Dominic, Barudžija, Tanja, Stevanović, Jasmina, Friedrich, Bernd, Jovićević, Jovan J., "Study of Nd deposition onto W and Mo Cathodes from Molten Oxide-Fluoride Electrolyte" in International Journal of Electrochemical Science, 15, no. 7 (2020):7039-7052,
https://doi.org/10.20964/2020.07.82 . .
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