A flat-lying dimer as a key intermediate in NO reduction on Cu(100)

Kenta Kuroishi; Muhammad Rifqi Al Fauzan; Thanh Ngoc Pham; Yuelin Wang; Yuji Hamamoto; Kouji Inagaki; Akitoshi Shiotari; Hiroshi Okuyama; Shinichiro Hatta; Tetsuya Aruga; Ikutaro Hamada; Yoshitada Morikawa

doi:10.1039/D1CP02746H

A flat-lying dimer as a key intermediate in NO reduction on Cu(100)†

Kenta Kuroishi,‡^a Muhammad Rifqi Al Fauzan,‡^bc Thanh Ngoc Pham,^b Yuelin Wang,^b Yuji Hamamoto,

^b Kouji Inagaki,

^b Akitoshi Shiotari,

§^a Hiroshi Okuyama,

*^a Shinichiro Hatta,

^a Tetsuya Aruga,

^a Ikutaro Hamada

^bd and Yoshitada Morikawa

^bde

Author affiliations

* Corresponding authors

^a Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan
E-mail: hokuyama@kuchem.kyoto-u.ac.jp

^b Department of Precision Engineering, Graduate School of Engineering, Osaka University, 2-1, Yamadaoka, Suita, Osaka 565-0871, Japan

^c Department of Electrical Engineering and Informatics, Vocational College, Universitas Gadjah Mada, Yogyakarta 55281, Indonesia

^d Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Goryo-Ohara, Nishikyou-ku, Katsura, Kyoto 615-8245, Japan

^e Research Center for Precision Engineering, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

Abstract

The reaction of nitric oxide (NO) on Cu(100) is studied by scanning tunneling microscopy, electron energy loss spectroscopy and density functional theory calculations. The NO molecules adsorb mainly as monomers at 64 K, and react and dissociate to yield oxygen atoms on the surface at ∼70 K. The temperature required for the dissociation is significantly low for Cu(100), compared to those for Cu(111) and Cu(110). The minimum energy pathway of the reaction is via (NO)₂ formation, which converts into a flat-lying ONNO and then dissociates into N₂O and O with a considerably low activation energy. We propose that the formation of (NO)₂ and flat-lying ONNO is the key to the exceptionally high reactivity of NO on Cu(100).

Physical Chemistry Chemical Physics

A flat-lying dimer as a key intermediate in NO reduction on Cu(100)†

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