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Reactivity of Nitric Oxide on Copper Surfaces

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Abstract

Nitric oxide (NO or nitrogen monoxide) is a diatomic molecule consisting of a nitrogen atom and an oxygen atom. It is a free radical, i.e., a relatively stable molecule with an unpaired electron. Owing to its radical reactivity, NO is of considerable importance not only in chemical engineering and industry but also in medicine and physiology.

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Notes

  1. 1.

    This diagram is depicted based on energy diagrams of CO on transition metal surfaces [43, 44].

  2. 2.

    Experimental studies with photoemission spectroscopy (PES) [45, 46] and inverse photoemission spectroscopy (IPES) [9] show that the NO \(2\pi ^*\)-derived resonance states are detected at 2.1–2.6 eV below the Fermi level and 1.5–1.6 eV above the Fermi level, respectively.

  3. 3.

    Brodén et al. [57] also proposed the border between elements in the periodic table for the adsorption geometries of CO on metal surfaces; CO is dissociatively (molecularly) adsorbed onto surfaces of metals farther from the left-hand (right-hand) side of Fe, Tc, and W (Co, Ru, and Re). Later, Fielicke et al. [23] summarized more detailed data concerning the adsorption geometries of CO on each metal surface.

  4. 4.

    Close-packed surfaces means the (111) surfaces for face-centered cubic (fcc) metals (Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, and Au) and (0001) surfaces for hexagonal close-packed (hcp) metals (Co and Ru).

  5. 5.

    Sheppard and De La Cruz [17] did not refer to the N–O stretching energy of upright NO bonded to fourfold hollow sites, and therefore, no energy range of this species is shown in Fig. 1.6. On the other hand, for NO/Pd(001), RAIRS measurements [76] and DFT calculations [77] have been assigned the peak found between 1470 and 1512 cm\(^{-1}\) to the N–O stretching mode of upright NO bonded to the fourfold hollow site.

  6. 6.

    According to Gajdoš et al. [13], upright NO bonded to the atop site was calculated to be the most stable species on Ir(111), and bent NO bonded to the bridge site was calculated to be the most stable species on Au(111). Conversely, for NO/Au(111), later theoretical studies concluded that NO is preferably bonded to the atop site in a bent configuration (see Sect. 1.4.2).

  7. 7.

    This species is also known as a lying-down configuration or an inclined configuration.

  8. 8.

    For CO on transition metal surfaces, generally, the vibrational energies of C–O stretching modes lie in the range 1800 to 2100 cm\(^{-1}\) [22, 23]. In contrast, for CO/K/Rh(001) [83], CO/Cr(110) [84], and CO/Fe(001) [85, 86], vibrational peaks with much lower energies (in a range of 1150–1465 cm\(^{-1}\)) have been detected and assigned to flat-lying CO.

  9. 9.

    The upright and end-on configurations are sometimes described as U-shaped and C-shaped dimers, respectively.

  10. 10.

    The SCR of NO is a reaction where NO is selectively reduced together with the oxidation of hydrocarbons, such as alcohols or alkanes, to yield N\(_2\).

  11. 11.

    The DFT calculations [30] revealed that the molecule is in a bent configuration. However, the STM experiments cannot determine the configuration of the molecule (i.e., whether upright or bent configuration) because of molecular diffusion induced by the STM tip.

  12. 12.

    When a spin of magnetic adsorbates is screened by conduction electrons of the substrate (the Kondo–Yoshida singlet state), a resonance state, namely the Kondo resonance, appears near the Fermi level due to the many-body effect on flipping of the adsorbate spin [149].

  13. 13.

    An anti-absorption peak, a RAIRS peak with a negative intensity, arises from a RAIRS-inactive vibrational mode. The frustrated rotation mode of a bent NO is RAIRS-active whereas that of an upright NO is inactive. Therefore, the anti-absorption peak was ascribed to an upright NO [167].

  14. 14.

    For Cu(111), 1 ML = 1.76 \(\times \) 10\(^{15}\) molecules/cm\(^2\).

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    Akitoshi Shiotari

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Shiotari, A. (2017). Introduction. In: Reactivity of Nitric Oxide on Copper Surfaces. Springer Theses. Springer, Singapore. https://doi.org/10.1007/978-981-10-4582-0_1

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