Formation Mechanism and Hydrothermal Synthesis of Highly Active Ir1-xRuxO2 Nanoparticles for the Oxygen Evolution Reaction
Bertelsen, Andreas Dueholm ; Kløve, Magnus ; Broge, Nils Lau Nyborg ; Bondesgaard, Martin ; Stubkjær, Rasmus Baden ; Dippel, Ann Christin ; Li, Qinyu ; Tilley, Richard ; Vogel Jørgensen, Mads Ry LU
and Iversen, Bo Brummerstedt
(2024)
In Journal of the American Chemical Society
146(34).
p.23729-23740
- Abstract
Iridium dioxide (IrO2), ruthenium dioxide (RuO2), and their solid solutions (Ir1-xRuxO2) are very active electrocatalysts for the oxygen evolution reaction (OER). Efficient and facile synthesis of nanosized crystallites of these materials is of high significance for electrocatalytic applications for converting green energy to fuels (power-to-X). Here, we use in situ X-ray scattering to examine reaction conditions for different Ir and Ru precursors resulting in the development of a simple hydrothermal synthesis route using IrCl3 and KRuO4 to obtain homogeneous phase-pure Ir1-xRuxO2 nanocrystals. The solid solution nanocrystals... (More)
Iridium dioxide (IrO2), ruthenium dioxide (RuO2), and their solid solutions (Ir1-xRuxO2) are very active electrocatalysts for the oxygen evolution reaction (OER). Efficient and facile synthesis of nanosized crystallites of these materials is of high significance for electrocatalytic applications for converting green energy to fuels (power-to-X). Here, we use in situ X-ray scattering to examine reaction conditions for different Ir and Ru precursors resulting in the development of a simple hydrothermal synthesis route using IrCl3 and KRuO4 to obtain homogeneous phase-pure Ir1-xRuxO2 nanocrystals. The solid solution nanocrystals can be obtained with a tunable composition of 0.2 < x < 1.0 and with ultra-small coherently scattering crystalline domains estimated from 1.3 to 2.6 nm in diameter based on PDF refinements. The in situ X-ray scattering data reveal a two-step formation mechanism, which involves the initial loss of chloride ligands followed by the formation of metal-oxygen octahedra clusters containing both Ir and Ru. These octahedra assemble with time resulting in long-range order resembling the rutile structure. The mixing of the metals on the atomic scale during the crystal formation presumably allows the formation of the solid solution rather than heterogeneous mixtures. The size of the final nanocrystals can be controlled by tuning the synthesis temperature. The facile hydrothermal synthesis route provides ultra-small nanoparticles with activity toward the OER in acidic electrolytes comparable to the best in the literature, and the optimal material composition very favorably combines low overpotential, high mass activity, and increased stability.
(Less)
- author
- Bertelsen, Andreas Dueholm
; Kløve, Magnus
; Broge, Nils Lau Nyborg
; Bondesgaard, Martin
; Stubkjær, Rasmus Baden
; Dippel, Ann Christin
; Li, Qinyu
; Tilley, Richard
; Vogel Jørgensen, Mads Ry
LU
and Iversen, Bo Brummerstedt
- organization
- publishing date
- 2024-08
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of the American Chemical Society
- volume
- 146
- issue
- 34
- pages
- 12 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- pmid:39151091
- scopus:85202209458
- ISSN
- 0002-7863
- DOI
- 10.1021/jacs.4c04607
- language
- English
- LU publication?
- yes
- id
- 763d49c2-246b-4ebd-9e6b-746d82a7e22b
- date added to LUP
- 2024-10-30 15:20:47
- date last changed
- 2025-07-11 02:41:45
@article{763d49c2-246b-4ebd-9e6b-746d82a7e22b,
abstract = {{<p>Iridium dioxide (IrO<sub>2</sub>), ruthenium dioxide (RuO<sub>2</sub>), and their solid solutions (Ir<sub>1-x</sub>Ru<sub>x</sub>O<sub>2</sub>) are very active electrocatalysts for the oxygen evolution reaction (OER). Efficient and facile synthesis of nanosized crystallites of these materials is of high significance for electrocatalytic applications for converting green energy to fuels (power-to-X). Here, we use in situ X-ray scattering to examine reaction conditions for different Ir and Ru precursors resulting in the development of a simple hydrothermal synthesis route using IrCl<sub>3</sub> and KRuO<sub>4</sub> to obtain homogeneous phase-pure Ir<sub>1-x</sub>Ru<sub>x</sub>O<sub>2</sub> nanocrystals. The solid solution nanocrystals can be obtained with a tunable composition of 0.2 < x < 1.0 and with ultra-small coherently scattering crystalline domains estimated from 1.3 to 2.6 nm in diameter based on PDF refinements. The in situ X-ray scattering data reveal a two-step formation mechanism, which involves the initial loss of chloride ligands followed by the formation of metal-oxygen octahedra clusters containing both Ir and Ru. These octahedra assemble with time resulting in long-range order resembling the rutile structure. The mixing of the metals on the atomic scale during the crystal formation presumably allows the formation of the solid solution rather than heterogeneous mixtures. The size of the final nanocrystals can be controlled by tuning the synthesis temperature. The facile hydrothermal synthesis route provides ultra-small nanoparticles with activity toward the OER in acidic electrolytes comparable to the best in the literature, and the optimal material composition very favorably combines low overpotential, high mass activity, and increased stability.</p>}},
author = {{Bertelsen, Andreas Dueholm and Kløve, Magnus and Broge, Nils Lau Nyborg and Bondesgaard, Martin and Stubkjær, Rasmus Baden and Dippel, Ann Christin and Li, Qinyu and Tilley, Richard and Vogel Jørgensen, Mads Ry and Iversen, Bo Brummerstedt}},
issn = {{0002-7863}},
language = {{eng}},
number = {{34}},
pages = {{23729--23740}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Journal of the American Chemical Society}},
title = {{Formation Mechanism and Hydrothermal Synthesis of Highly Active Ir<sub>1-x</sub>Ru<sub>x</sub>O<sub>2</sub> Nanoparticles for the Oxygen Evolution Reaction}},
url = {{http://dx.doi.org/10.1021/jacs.4c04607}},
doi = {{10.1021/jacs.4c04607}},
volume = {{146}},
year = {{2024}},
}