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Issue 20, 2020
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Interphase-oxidized ruthenium metal with half-filled d-orbitals for hydrogen oxidation in an alkaline solution

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Abstract

Ruthenium is generally used as a property-promoter rather than as the main catalyst for the hydrogen oxidation reaction (HOR) because of the preferential formation of Ru–O(H) at a relatively low anode potential (0.1–0.3 V vs. the reversible hydrogen electrode, RHE), which leads to few oxide-free Ru atoms remaining for bonding to H intermediates. Here, we report an uncommon finding that sub-2 nm Ru clusters can efficiently catalyze the HOR at a potential of up to 0.9 V (vs. RHE) without being oxidized, when the Ru clusters are interphase-oxidized by TiO2 to yield nearly half-filled 4d-orbitals (IO-Ru–TiO2/C). The X-ray absorption and X-ray photoelectron spectroscopy results confirmed that the Ru clusters in IO-Ru–TiO2/C are preoxidized close to a level of RuIV and maintain a metallic surface with abundant metallic Ru–Ru bonds. These features decrease the adsorption of oxygen species during the HOR and greatly promote HOR activity and inoxidizability under alkaline conditions. As a result, a mass activity of 907 A g−1 Ru @ 0.05 V is achieved for the IO-Ru–TiO2/C catalyst, which is 17.5 and 1.5 times greater than those of Ru/C and PtRu/C catalysts, respectively, ranking it among the most active HOR catalysts in alkaline media reported to date.

Graphical abstract: Interphase-oxidized ruthenium metal with half-filled d-orbitals for hydrogen oxidation in an alkaline solution

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Supplementary files

Article information


Submitted
04 Mar 2020
Accepted
29 Apr 2020
First published
29 Apr 2020

J. Mater. Chem. A, 2020,8, 10168-10174
Article type
Communication

Interphase-oxidized ruthenium metal with half-filled d-orbitals for hydrogen oxidation in an alkaline solution

J. Jiang, S. Tao, Q. He, J. Wang, Y. Zhou, Z. Xie, W. Ding and Z. Wei, J. Mater. Chem. A, 2020, 8, 10168
DOI: 10.1039/D0TA02528C

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