Improved activity for the oxygen evolution reaction using a tiara-like thiolate-protected nickel nanocluster

Sota Funaki; Tokuhisa Kawawaki; Tomoshige Okada; Kana Takemae; Sakiat Hossain; Yoshiki Niihori; Takumi Naito; Makito Takagi; Tomomi Shimazaki; Soichi Kikkawa; Seiji Yamazoe; Masanori Tachikawa; Yuichi Negishi

doi:10.1039/D2NR06952K

Improved activity for the oxygen evolution reaction using a tiara-like thiolate-protected nickel nanocluster†

Sota Funaki,^a Tokuhisa Kawawaki,

*^ab Tomoshige Okada,^a Kana Takemae,^a Sakiat Hossain,

^b Yoshiki Niihori,

^b Takumi Naito,^c Makito Takagi,

^c Tomomi Shimazaki,

^c Soichi Kikkawa,

^d Seiji Yamazoe,

^d Masanori Tachikawa

^c and Yuichi Negishi

*^ab

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* Corresponding authors

^a Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
E-mail: kawawaki@rs.tus.ac.jp, negishi@rs.tus.ac.jp
Fax: +81-3-5261-4631
Tel: +81-3-5228-9145

^b Research Institute for Science and Technology, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan

^c Graduate School of NanoBioScience, Yokohama City University, 22-2 Seto, Kanazawa-ku, Yokohama 236-0027, Japan

^d Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji-shi, Tokyo 192-0397, Japan

Abstract

Practical electrochemical water splitting and carbon-dioxide reduction are desirable for a sustainable energy society. In particular, facilitating the oxygen evolution reaction (OER, the reaction at the anode) will increase the efficiency of these reactions. Nickel (Ni) compounds are excellent OER catalysts under basic conditions, and atomically precise Ni clusters have been actively studied to understand their complex reaction mechanisms. In this study, we evaluated the geometric/electronic structure of tiara-like metal nanoclusters [Ni_n(PET)_2n; n = 4, 5, 6, where PET refers to phenylethanethiolate] with the same SR ligand. The geometric structure of Ni₅(SR)₁₀ was determined for the first time using single-crystal X-ray diffraction. Additionally, combined electrochemical measurements and X-ray absorption fine structure measurements revealed that Ni₅(SR)₁₀ easily forms an OER intermediate and therefore exhibits a high specific activity.

Nanoscale

Improved activity for the oxygen evolution reaction using a tiara-like thiolate-protected nickel nanocluster†

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Improved activity for the oxygen evolution reaction using a tiara-like thiolate-protected nickel nanocluster

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