Schmuki, Patrik

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TiO2 nanotube arrays decorated with Ir nanoparticles for enhanced hydrogen evolution electrocatalysis

Lačnjevac, Uroš; Vasilic, Rastko; Dobrota, Ana S.; Đurđić, Slađana; Tomanec, Ondřej; Zbořil, Radek; Mohajernia, Shiva; Nguyen, Nhat Truong; Skorodumova, Natalia; Manojlović, Dragan; Elezović, Nevenka R.; Pasti, Igor; Schmuki, Patrik

(Belgrade : Institute for Multidisciplinary Research, 2023)

TY  - CONF
AU  - Lačnjevac, Uroš
AU  - Vasilic, Rastko
AU  - Dobrota, Ana S.
AU  - Đurđić, Slađana
AU  - Tomanec, Ondřej
AU  - Zbořil, Radek
AU  - Mohajernia, Shiva
AU  - Nguyen, Nhat Truong
AU  - Skorodumova, Natalia
AU  - Manojlović, Dragan
AU  - Elezović, Nevenka R.
AU  - Pasti, Igor
AU  - Schmuki, Patrik
PY  - 2023
UR  - http://rimsi.imsi.bg.ac.rs/handle/123456789/2843
AB  - Designing cost-effective hydrogen evolution reaction (HER) electrocatalysts containing highly active, but expensive platinum group metals (PGMs) is key to the commercialization of polymer electrolyte membrane water electrolysis systems for green hydrogen production. Our recent investigations have shown that efficient and durable HER composite cathodes can be prepared by spontaneous deposition of PGM nanoparticles on self-aligned titania nanotube (TNT) arrays formed by anodization [1]. In this synthesis route, anatase TNTs are first cathodically protonated (H-TNT), and then used as the reducing agent for PGM ions at room temperature. Herein, we employ the galvanic displacement strategy to decorate H-TNT arrays with ultrafine Ir nanoparticles [2]. We demonstrate that transforming the top surface morphology of supporting TNT arrays from ordered open-top tubes to bundled nanowires (“nanograss”) is beneficial for exposing more Ir active centers during the HER operation. Consequently, applying very low concentrations of Ir(III) ions in the galvanic displacement step is sufficient to produce exceptionally active nanograss-modified Ir@TNT composites. An optimum Ir@TNT, possessing a low Ir loading of 5.7 μgIr cm–2, requires an overpotential of only –63 mV to reach a current density of –100 mA cm–2 and shows a stable long-term performance in a 1 M HClO4 solution. Computational simulations suggest that the hydrogen-rich TiO2 support not only strongly interacts with anchored Ir particles and weakens their H binding strength to a moderate level, but also actively provides hydrogen for rejuvenation of the Ir active sites at the Ir|H-TiO2 interface, thereby significantly enhancing HER catalysis.

[1] U.Č. Lačnjevac, R. Vasilić, T. Tokarski, G. Cios, P. Żabiński, N. Elezović and N. V. Krstajić, Nano Energy 47 (2018) 527.
[2] U. Lačnjevac, R. Vasilić, A. Dobrota, S. Đurđić, O. Tomanec, R. Zbořil, S. Mohajernia, N.T. Nguyen, N. Skorodumova, D. Manojlović, N. Elezović, I. Pašti, P. Schmuki, Journal of Materials Chemistry A 8 (2020) 22773.
PB  - Belgrade : Institute for Multidisciplinary Research
C3  - Programme and the Book of Abstracts / 7th Conference of The Serbian Society for Ceramic Materials, 7CSCS-2023, June 14-16, 2023 Belgrade, Serbia
T1  - TiO2 nanotube arrays decorated with Ir nanoparticles for enhanced hydrogen evolution electrocatalysis
EP  - 74
SP  - 73
UR  - https://hdl.handle.net/21.15107/rcub_rimsi_2843
ER  - 
@conference{
author = "Lačnjevac, Uroš and Vasilic, Rastko and Dobrota, Ana S. and Đurđić, Slađana and Tomanec, Ondřej and Zbořil, Radek and Mohajernia, Shiva and Nguyen, Nhat Truong and Skorodumova, Natalia and Manojlović, Dragan and Elezović, Nevenka R. and Pasti, Igor and Schmuki, Patrik",
year = "2023",
abstract = "Designing cost-effective hydrogen evolution reaction (HER) electrocatalysts containing highly active, but expensive platinum group metals (PGMs) is key to the commercialization of polymer electrolyte membrane water electrolysis systems for green hydrogen production. Our recent investigations have shown that efficient and durable HER composite cathodes can be prepared by spontaneous deposition of PGM nanoparticles on self-aligned titania nanotube (TNT) arrays formed by anodization [1]. In this synthesis route, anatase TNTs are first cathodically protonated (H-TNT), and then used as the reducing agent for PGM ions at room temperature. Herein, we employ the galvanic displacement strategy to decorate H-TNT arrays with ultrafine Ir nanoparticles [2]. We demonstrate that transforming the top surface morphology of supporting TNT arrays from ordered open-top tubes to bundled nanowires (“nanograss”) is beneficial for exposing more Ir active centers during the HER operation. Consequently, applying very low concentrations of Ir(III) ions in the galvanic displacement step is sufficient to produce exceptionally active nanograss-modified Ir@TNT composites. An optimum Ir@TNT, possessing a low Ir loading of 5.7 μgIr cm–2, requires an overpotential of only –63 mV to reach a current density of –100 mA cm–2 and shows a stable long-term performance in a 1 M HClO4 solution. Computational simulations suggest that the hydrogen-rich TiO2 support not only strongly interacts with anchored Ir particles and weakens their H binding strength to a moderate level, but also actively provides hydrogen for rejuvenation of the Ir active sites at the Ir|H-TiO2 interface, thereby significantly enhancing HER catalysis.

[1] U.Č. Lačnjevac, R. Vasilić, T. Tokarski, G. Cios, P. Żabiński, N. Elezović and N. V. Krstajić, Nano Energy 47 (2018) 527.
[2] U. Lačnjevac, R. Vasilić, A. Dobrota, S. Đurđić, O. Tomanec, R. Zbořil, S. Mohajernia, N.T. Nguyen, N. Skorodumova, D. Manojlović, N. Elezović, I. Pašti, P. Schmuki, Journal of Materials Chemistry A 8 (2020) 22773.",
publisher = "Belgrade : Institute for Multidisciplinary Research",
journal = "Programme and the Book of Abstracts / 7th Conference of The Serbian Society for Ceramic Materials, 7CSCS-2023, June 14-16, 2023 Belgrade, Serbia",
title = "TiO2 nanotube arrays decorated with Ir nanoparticles for enhanced hydrogen evolution electrocatalysis",
pages = "74-73",
url = "https://hdl.handle.net/21.15107/rcub_rimsi_2843"
}
Lačnjevac, U., Vasilic, R., Dobrota, A. S., Đurđić, S., Tomanec, O., Zbořil, R., Mohajernia, S., Nguyen, N. T., Skorodumova, N., Manojlović, D., Elezović, N. R., Pasti, I.,& Schmuki, P.. (2023). TiO2 nanotube arrays decorated with Ir nanoparticles for enhanced hydrogen evolution electrocatalysis. in Programme and the Book of Abstracts / 7th Conference of The Serbian Society for Ceramic Materials, 7CSCS-2023, June 14-16, 2023 Belgrade, Serbia
Belgrade : Institute for Multidisciplinary Research., 73-74.
https://hdl.handle.net/21.15107/rcub_rimsi_2843
Lačnjevac U, Vasilic R, Dobrota AS, Đurđić S, Tomanec O, Zbořil R, Mohajernia S, Nguyen NT, Skorodumova N, Manojlović D, Elezović NR, Pasti I, Schmuki P. TiO2 nanotube arrays decorated with Ir nanoparticles for enhanced hydrogen evolution electrocatalysis. in Programme and the Book of Abstracts / 7th Conference of The Serbian Society for Ceramic Materials, 7CSCS-2023, June 14-16, 2023 Belgrade, Serbia. 2023;:73-74.
https://hdl.handle.net/21.15107/rcub_rimsi_2843 .
Lačnjevac, Uroš, Vasilic, Rastko, Dobrota, Ana S., Đurđić, Slađana, Tomanec, Ondřej, Zbořil, Radek, Mohajernia, Shiva, Nguyen, Nhat Truong, Skorodumova, Natalia, Manojlović, Dragan, Elezović, Nevenka R., Pasti, Igor, Schmuki, Patrik, "TiO2 nanotube arrays decorated with Ir nanoparticles for enhanced hydrogen evolution electrocatalysis" in Programme and the Book of Abstracts / 7th Conference of The Serbian Society for Ceramic Materials, 7CSCS-2023, June 14-16, 2023 Belgrade, Serbia (2023):73-74,
https://hdl.handle.net/21.15107/rcub_rimsi_2843 .