RatioCAT - Rational Design of Multifunctional Electrode Interfaces for Efficient Electrocatalytic Hydrogen Production

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RatioCAT - Rational Design of Multifunctional Electrode Interfaces for Efficient Electrocatalytic Hydrogen Production (en)
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Ru–Co alloy coatings electrodeposited on a MAX phase substrate as efficient catalysts for the hydrogen evolution reaction

Kutyła, Dawid; Krstajić Pajić, Mila N.; Lačnjevac, Uroš Č.; Marzec, Mateusz M.; Elezović, Nevenka R.; Żabiński, Piotr

(Elsevier Ltd., 2024)

TY  - JOUR
AU  - Kutyła, Dawid
AU  - Krstajić Pajić, Mila N.
AU  - Lačnjevac, Uroš Č.
AU  - Marzec, Mateusz M.
AU  - Elezović, Nevenka R.
AU  - Żabiński, Piotr
PY  - 2024
UR  - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/6992
AB  - This study investigates the structure, electrochemical behavior and hydrogen evolution reaction (HER) performance of electrodeposited Ru–Co alloy coatings. The alloys were prepared from a 0.75 M Co2+ + 0.025 M Ru3+ solution at various potentials ranging from −0.5 to −1.2 V vs. SCE. Results reveal that the Ru and Co deposition processes are interdependent. The deposition of nobler Ru from the mixed metal solution reaches pure diffusion control already at −0.7 V compared to −1.0 V from a single Ru bath. On the other hand, Co deposition is significantly facilitated in the presence of Ru in the solution. Consequently, as the deposition potential changes from −0.6 to −1.0 V, Ru–Co solid solution coatings characterized by a distinct globular morphology are formed, with their Co content increasing from 22.1/7.4 to 70.2/86.1 wt% for the Cu/Ti2AlC MAX phase substrate applied. The alloy catalysts are found to show much better HER activity and stability in alkaline than in acidic solutions. The best Ru–Co@Ti2AlC sample, electrodeposited at −0.6 V, requires an overpotential of only −95 mV to deliver a current density of −100 mA cm−2 in 1 M KOH, thus outperforming most Ru–Co-based HER electrocatalysts reported to date.
PB  - Elsevier Ltd.
T2  - International Journal of Hydrogen Energy
T1  - Ru–Co alloy coatings electrodeposited on a MAX phase substrate as efficient catalysts for the hydrogen evolution reaction
EP  - 40
SP  - 28
VL  - 56
DO  - 10.1016/j.ijhydene.2023.11.296
ER  - 
@article{
author = "Kutyła, Dawid and Krstajić Pajić, Mila N. and Lačnjevac, Uroš Č. and Marzec, Mateusz M. and Elezović, Nevenka R. and Żabiński, Piotr",
year = "2024",
abstract = "This study investigates the structure, electrochemical behavior and hydrogen evolution reaction (HER) performance of electrodeposited Ru–Co alloy coatings. The alloys were prepared from a 0.75 M Co2+ + 0.025 M Ru3+ solution at various potentials ranging from −0.5 to −1.2 V vs. SCE. Results reveal that the Ru and Co deposition processes are interdependent. The deposition of nobler Ru from the mixed metal solution reaches pure diffusion control already at −0.7 V compared to −1.0 V from a single Ru bath. On the other hand, Co deposition is significantly facilitated in the presence of Ru in the solution. Consequently, as the deposition potential changes from −0.6 to −1.0 V, Ru–Co solid solution coatings characterized by a distinct globular morphology are formed, with their Co content increasing from 22.1/7.4 to 70.2/86.1 wt% for the Cu/Ti2AlC MAX phase substrate applied. The alloy catalysts are found to show much better HER activity and stability in alkaline than in acidic solutions. The best Ru–Co@Ti2AlC sample, electrodeposited at −0.6 V, requires an overpotential of only −95 mV to deliver a current density of −100 mA cm−2 in 1 M KOH, thus outperforming most Ru–Co-based HER electrocatalysts reported to date.",
publisher = "Elsevier Ltd.",
journal = "International Journal of Hydrogen Energy",
title = "Ru–Co alloy coatings electrodeposited on a MAX phase substrate as efficient catalysts for the hydrogen evolution reaction",
pages = "40-28",
volume = "56",
doi = "10.1016/j.ijhydene.2023.11.296"
}
Kutyła, D., Krstajić Pajić, M. N., Lačnjevac, U. Č., Marzec, M. M., Elezović, N. R.,& Żabiński, P.. (2024). Ru–Co alloy coatings electrodeposited on a MAX phase substrate as efficient catalysts for the hydrogen evolution reaction. in International Journal of Hydrogen Energy
Elsevier Ltd.., 56, 28-40.
https://doi.org/10.1016/j.ijhydene.2023.11.296
Kutyła D, Krstajić Pajić MN, Lačnjevac UČ, Marzec MM, Elezović NR, Żabiński P. Ru–Co alloy coatings electrodeposited on a MAX phase substrate as efficient catalysts for the hydrogen evolution reaction. in International Journal of Hydrogen Energy. 2024;56:28-40.
doi:10.1016/j.ijhydene.2023.11.296 .
Kutyła, Dawid, Krstajić Pajić, Mila N., Lačnjevac, Uroš Č., Marzec, Mateusz M., Elezović, Nevenka R., Żabiński, Piotr, "Ru–Co alloy coatings electrodeposited on a MAX phase substrate as efficient catalysts for the hydrogen evolution reaction" in International Journal of Hydrogen Energy, 56 (2024):28-40,
https://doi.org/10.1016/j.ijhydene.2023.11.296 . .
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Activation of Osmium by the Surface Effects of Hydrogenated TiO2 Nanotube Arrays for Enhanced Hydrogen Evolution Reaction Performance

Krstajić Pajić, Mila N.; Dobrota, Ana S.; Mazare, Anca; Đurđić, Slađana; Hwang, Imgon; Skorodumova, Natalia V.; Manojlović, Dragan; Vasilić, Rastko; Pašti, Igor A.; Schmuki, Patrik; Lačnjevac, Uroš

(American Chemical Society, 2023)

TY  - JOUR
AU  - Krstajić Pajić, Mila N.
AU  - Dobrota, Ana S.
AU  - Mazare, Anca
AU  - Đurđić, Slađana
AU  - Hwang, Imgon
AU  - Skorodumova, Natalia V.
AU  - Manojlović, Dragan
AU  - Vasilić, Rastko
AU  - Pašti, Igor A.
AU  - Schmuki, Patrik
AU  - Lačnjevac, Uroš
PY  - 2023
UR  - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/6576
AB  - Efficient cathodes for the hydrogen evolution reaction (HER) in acidic water electrolysis rely on the use of expensive platinum group metals (PGMs). However, to achieve economically viable operation, both the content of PGMs must be reduced and their intrinsically strong H adsorption mitigated. Herein, we show that the surface effects of hydrogenated TiO2 nanotube (TNT) arrays can make osmium, a so far less-explored PGM, a highly active HER electrocatalyst. These defect-rich TiO2 nanostructures provide an interactive scaffold for the galvanic deposition of Os particles with modulated adsorption properties. Through systematic investigations, we identify the synthesis conditions (OsCl3 concentration/temperature/reaction time) that yield a progressive improvement in Os deposition rate and mass loading, thereby decreasing the HER overpotential. At the same time, the Os particles deposited by this procedure remain mainly sub-nanometric and entirely cover the inner tube walls. An optimally balanced Os@TNT composite prepared at 3 mM/55 °C/30 min exhibits a record low overpotential (η) of 61 mV at a current density of 100 mA cm-2, a high mass activity of 20.8 A mgOs-1 at 80 mV, and a stable performance in an acidic medium. Density functional theory calculations indicate the existence of strong interactions between the hydrogenated TiO2 surface and small Os clusters, which may weaken the Os-H* binding strength and thus boost the intrinsic HER activity of Os centers. The results presented in this study offer new directions for the fabrication of cost-effective PGM-based catalysts and a better understanding of the synergistic electronic interactions at the PGM|TiO2 interface.
PB  - American Chemical Society
T1  - Activation of Osmium by the Surface Effects of Hydrogenated TiO2 Nanotube Arrays for Enhanced Hydrogen Evolution Reaction Performance
EP  - 31469
IS  - 26
SP  - 31459
VL  - 15
DO  - 10.1021/acsami.3c04498
ER  - 
@article{
author = "Krstajić Pajić, Mila N. and Dobrota, Ana S. and Mazare, Anca and Đurđić, Slađana and Hwang, Imgon and Skorodumova, Natalia V. and Manojlović, Dragan and Vasilić, Rastko and Pašti, Igor A. and Schmuki, Patrik and Lačnjevac, Uroš",
year = "2023",
abstract = "Efficient cathodes for the hydrogen evolution reaction (HER) in acidic water electrolysis rely on the use of expensive platinum group metals (PGMs). However, to achieve economically viable operation, both the content of PGMs must be reduced and their intrinsically strong H adsorption mitigated. Herein, we show that the surface effects of hydrogenated TiO2 nanotube (TNT) arrays can make osmium, a so far less-explored PGM, a highly active HER electrocatalyst. These defect-rich TiO2 nanostructures provide an interactive scaffold for the galvanic deposition of Os particles with modulated adsorption properties. Through systematic investigations, we identify the synthesis conditions (OsCl3 concentration/temperature/reaction time) that yield a progressive improvement in Os deposition rate and mass loading, thereby decreasing the HER overpotential. At the same time, the Os particles deposited by this procedure remain mainly sub-nanometric and entirely cover the inner tube walls. An optimally balanced Os@TNT composite prepared at 3 mM/55 °C/30 min exhibits a record low overpotential (η) of 61 mV at a current density of 100 mA cm-2, a high mass activity of 20.8 A mgOs-1 at 80 mV, and a stable performance in an acidic medium. Density functional theory calculations indicate the existence of strong interactions between the hydrogenated TiO2 surface and small Os clusters, which may weaken the Os-H* binding strength and thus boost the intrinsic HER activity of Os centers. The results presented in this study offer new directions for the fabrication of cost-effective PGM-based catalysts and a better understanding of the synergistic electronic interactions at the PGM|TiO2 interface.",
publisher = "American Chemical Society",
title = "Activation of Osmium by the Surface Effects of Hydrogenated TiO2 Nanotube Arrays for Enhanced Hydrogen Evolution Reaction Performance",
pages = "31469-31459",
number = "26",
volume = "15",
doi = "10.1021/acsami.3c04498"
}
Krstajić Pajić, M. N., Dobrota, A. S., Mazare, A., Đurđić, S., Hwang, I., Skorodumova, N. V., Manojlović, D., Vasilić, R., Pašti, I. A., Schmuki, P.,& Lačnjevac, U.. (2023). Activation of Osmium by the Surface Effects of Hydrogenated TiO2 Nanotube Arrays for Enhanced Hydrogen Evolution Reaction Performance. 
American Chemical Society., 15(26), 31459-31469.
https://doi.org/10.1021/acsami.3c04498
Krstajić Pajić MN, Dobrota AS, Mazare A, Đurđić S, Hwang I, Skorodumova NV, Manojlović D, Vasilić R, Pašti IA, Schmuki P, Lačnjevac U. Activation of Osmium by the Surface Effects of Hydrogenated TiO2 Nanotube Arrays for Enhanced Hydrogen Evolution Reaction Performance. 2023;15(26):31459-31469.
doi:10.1021/acsami.3c04498 .
Krstajić Pajić, Mila N., Dobrota, Ana S., Mazare, Anca, Đurđić, Slađana, Hwang, Imgon, Skorodumova, Natalia V., Manojlović, Dragan, Vasilić, Rastko, Pašti, Igor A., Schmuki, Patrik, Lačnjevac, Uroš, "Activation of Osmium by the Surface Effects of Hydrogenated TiO2 Nanotube Arrays for Enhanced Hydrogen Evolution Reaction Performance", 15, no. 26 (2023):31459-31469,
https://doi.org/10.1021/acsami.3c04498 . .
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