Benzotriazole (BTAH) has been used
as a copper corrosion inhibitor
since the 1950s. However, the molecular level detail of how adsorption
and surface passivation occur remains a matter of debate. BTAH adsorption
on a Cu(111) single crystal has been investigated from medium coverage
to multilayer using scanning tunneling microscopy (STM), temperature-programmed
desorption (TPD), high resolution electron energy loss (HREEL) spectroscopy
and supporting density functional theory (DFT) calculations. Both
physisorbed and chemisorbed phases are observed. One extended and
highly ordered self-assembled metal−organic phase is seen
at saturation coverage and above. A metastable phase is also observed.
Complete desorption occurs at ca. 600 K. Those structures are critically
discussed in the light of some of the various adsorption models reported
in the literature and an alternative adsorption model is proposed.
These results allow a further understanding of the interaction between
benzotriazole and copper and, in turn, may help understanding the
mechanism for protection of copper and copper alloys from corrosion,
substantially contributing to a long-standing debate.
Benzotriazole (BTAH) has been used as a copper corrosion inhibitor since the 1950s; however, the molecular level detail of how inhibition occurs remains a matter of debate. The onset of BTAH adsorption on a Cu(111) single crystal was investigated via scanning tunnelling microscopy (STM), vibrational spectroscopy (RAIRS) and supporting DFT modelling. BTAH adsorbs as anionic (BTA(-)), CuBTA is a minority species, while Cu(BTA)2, the majority of the adsorbed species, form chains, whose sections appear to diffuse in a concerted manner. The copper surface appears to reconstruct in a (2 × 1) fashion.
The interaction of ethene with the Pd(110) surface has been investigated, mainly with a view to understanding the dehydrogenation reactions of the molecule and mainly using a molecular beam reactor. Ethene adsorbs with a high probability over the temperature range 130 to 800 K with the low-coverage sticking probability dropping from 0.8 at 130 K to 0.35 at 800 K. The adsorption is of the precursor type, with a weakly held form of ethene being the intermediate between the gas phase and strong chemisorption. Dehydrogenation begins at approximately 300 K and is fast above 350 K. If adsorption is carried out at temperatures up to approximately 380 K, adsorption saturates after about 0.25 monolayer have adsorbed, but above approximately 450 K, adsorption continues at a high rate with continuous hydrogen evolution and C deposition onto the surface. It appears that, in the intermediate temperature range, the carbonaceous species formed is located in the top layer and thus interferes with adsorption, whereas the C goes subsurface above 450 K, the adsorption is almost unaffected, and the C signal is significantly attenuated in XPS. However, the deposited carbon can easily be removed again by reaction with oxygen, thus implying that the carbon remains in the selvedge, that is, in the immediate subsurface region probably consisting of a few atomic layers. No well-ordered structures are identified in either LEED or STM, though some evidence of a c(2 x 2) structure can be seen. The Pd surface, at least above 450 K, appears to act as a "sponge" for carbon atoms, and this effect is also seen for the adsorption of other hydrocarbons such as acetaldehyde and acetic acid.
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