Acetaldehyde Chemistry on Ag{111}-(4 × 4)-Ag_1.83O between 77 and 200 K Studied by STM

Abstract

The interaction of acetaldehyde with the Ag{111}-(4 × 4)-Ag1.83O surface oxide structure at temperatures between 77 and 200 K has been studied with scanning tunneling microscopy at 5 K. The bonding sites, relative to the oxide structure, of acetaldehyde at 77 K, and of acetate and ethane-1,1-dioxy formed after annealing to 170 K are discussed. Helical polyacetaldehyde chains formed at 140 K, previously proposed on the basis of RAIRS data, have been observed directly, coexisting with the oxide surface.

Exploring the Self-Assembly Behaviors of an Organic Molecule Functionalized by Terminal Alkyne and Aldehyde Groups on Au(111)

“…Figure a) Organic molecules functionalized with the terminal alkyne group have been recently investigated to construct on-surface nanostructures and found to form “magic” clusters and network structures, where the intermolecular interactions are the CH/π bonding originated from the terminal alkyne groups. The reason for forming such specific surface nanostructures lies in the directionality of the CH/π bonding, where the electron-rich C–C triple bond can act as an electron donor and the C–H moiety plays the role of electron acceptor. , The aldehyde groups could also yield a relatively weak intermolecular hydrogen bonding, which has been investigated in our recent work and also reported by other groups . Due to the similar mechanism (i.e., intermolecular charge transfer) and similar bonding strength (at the level of weak hydrogen bonding) of these two kinds of attractive interactions, this system could also serve as a prototype for investigating the competitive or cooperative role between the alkyne and aldehyde groups in forming intermolecular interactions.…”

“…To unravel the formation mechanism of the self-assembled nanostructure and the interplay of the aldehyde and alkyne groups within the nanostructure, we have performed a series of detailed DFT calculations. First, we have calculated different binding ways of two EBA monomers as shown in Figure , which could be categorized as follows: (1) intermolecular hydrogen bonding between two aldehyde groups; , (2) CH/π bonding between two alkyne groups; , (3) intermolecular π–π interactions between two alkyne groups; and (4) intermolecular hydrogen bonding between the aldehyde and alkyne groups, which has not been demonstrated on surfaces so far. The most stable dimer structure involving intermolecular hydrogen bonding between two aldehyde groups has been shown (di1 in Figure ) and yields a binding energy of 0.186 eV.…”

“…21,23 The aldehyde groups could also yield a relatively weak intermolecular hydrogen bonding, which has been investigated in our recent work 24 and also reported by other groups. 25 Due to the similar mechanism (i.e., intermolecular charge transfer) and similar bonding strength (at the level of weak hydrogen bonding) of these two kinds of attractive interactions, this system could also serve as a prototype for investigating the competitive or cooperative role between the alkyne and aldehyde groups in forming intermolecular interactions.…”

Experimental and theoretical study of oxygen adsorption structures on Ag(111)

“…This method has also been used in a variety of subsequent studies. 11,12,43,54,63,70,71,72,73,74,75,76 Here we do not present any results obtained on samples prepared by this NO 2 method, although we did carry out a limited number of such studies. Consistent with Carlisle et al, 12 we were able to produce the atomic oxygen, p(4 × 5 √ 3)rect-O, and p(4 × 4)-O phases in these studies, which indicates that the use of NO 2 instead of atomic or molecular oxygen does not significantly change the picture drawn up here.…”

Control of selectivity in allylic alcohol oxidation on gold surfaces: the role of oxygen adatoms and hydroxyl species

“…The interaction of acetaldehyde with oxygen on silver surfaces has been shown to result in the formation of ethane-1,1-dioxy, 62,63 a bidentate intermediate that dehydrogenates to generate surface acetate. Surface acetates decompose on the Ag(110) surface in the presence of oxygen at B400 K to yield combustion products 64 a temperature very close to what we observed for allyl alcohol combustion on O/Au(111).…”