Activation of Osmium by the Surface Effects of Hydrogenated TiO2 Nanotube Arrays for Enhanced Hydrogen Evolution Reaction Performance
Samo za registrovane korisnike
2023
Autori
Krstajić Pajić, Mila N.Dobrota, Ana S.
Mazare, Anca
Đurđić, Slađana
Hwang, Imgon
Skorodumova, Natalia V.
Manojlović, Dragan
Vasilic, Rastko
Pašti, Igor A.
Schmuki, Patrik
Lačnjevac, Uroš
Članak u časopisu (Objavljena verzija)
Metapodaci
Prikaz svih podataka o dokumentuApstrakt
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.
Ključne reči:
platinum group metals / metal-support interactions / density functional theory / galvanic deposition / mass activityIzvor:
ACS Applied Materials and Interfaces, 2023, 15, 26, 31459-31469Izdavač:
- American Chemical Society
Finansiranje / projekti:
- RatioCAT - Rational Design of Multifunctional Electrode Interfaces for Efficient Electrocatalytic Hydrogen Production (RS-ScienceFundRS-Promis-6062244)
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200053 (Univerzitet u Beogradu, Institut za multidisciplinarna istraživanja) (RS-MESTD-inst-2020-200053)
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200135 (Univerzitet u Beogradu, Tehnološko-metalurški fakultet) (RS-MESTD-inst-2020-200135)
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200146 (Univerzitet u Beogradu, Fakultet za fizičku hemiju) (RS-MESTD-inst-2020-200146)
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200162 (Univerzitet u Beogradu, Fizički fakultet) (RS-MESTD-inst-2020-200162)
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200168 (Univerzitet u Beogradu, Hemijski fakultet) (RS-MESTD-inst-2020-200168)
- Bilateral cooperation program between the Republic of Serbia and the Federal Republic of Germany (project years 2020−2021, project no. 22)
- DFG
- Operational Program Research, Development and Education (European Regional Development Fund, project no. CZ.02.1.01/0.0/0.0/15_003/0000416 of the Ministry of Education, Youth and Sports of the Czech Republic)
- Swedish Research Council through grant agreement no. 2018- 05973
- Schwäbisch Gmünd Scientific Exchange Grant
Institucija/grupa
Institut za multidisciplinarna istraživanjaTY - 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 - Vasilic, Rastko AU - Pašti, Igor A. AU - Schmuki, Patrik AU - Lačnjevac, Uroš PY - 2023 UR - http://rimsi.imsi.bg.ac.rs/handle/123456789/2706 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 T2 - ACS Applied Materials and Interfaces 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 Vasilic, 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", journal = "ACS Applied Materials and Interfaces", 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., Vasilic, 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. in ACS Applied Materials and Interfaces 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, Vasilic 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. in ACS Applied Materials and Interfaces. 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, Vasilic, 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" in ACS Applied Materials and Interfaces, 15, no. 26 (2023):31459-31469, https://doi.org/10.1021/acsami.3c04498 . .