Adsorption and desorption of benzene on Si(111)‐7 × 7 studied by scanning tunnelling microscopy

Kawasaki, T.; Sakai, Daisuke; Kishimoto, Hiroshi; Akbar, Ade Asneil; Ogawa, Takashi; Oshima, C.

doi:10.1002/sia.967

Cited by 26 publications

(37 citation statements)

References 8 publications

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“…The increase in desorption temperature of benzene with the increase in surface coverage of benzaldehyde cannot be solely attributed to the attractive interaction between the desorbing species because for similar amounts of benzene formed on P 0.4 −Ru(0001), we see a difference in the peak desorption temperatures. 70 These results suggest that the mechanism of decarbonylation on P 0.4 −Ru(0001) involves consequential interactions between surface intermediates.…”

Section: Resultsmentioning

confidence: 91%

Catalytic Hydrogen Transfer and Decarbonylation of Aromatic Aldehydes on Ru and Ru Phosphide Model Catalysts

2018

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Transition-metal and metal phosphide nanoparticles catalyze hydrogen-transfer steps that reduce biomass-derived aldehydes using either gaseous H2 or organic hydrogen donors (e.g., alcohols) and produce valuable chemicals and fuels to replace petroleum derivatives. Here, we study reactions of aromatic aldehydes (furfural, benzaldehyde) on Ru(0001) and P0.4–Ru(0001), a surface representative of the (0001) facet of Ru2P, to determine how the addition of phosphorus influences activation barriers and flux along competing reaction pathways. Although Ru(0001) entirely decomposes furfural to CO, H2, and surface carbon, P0.4–Ru(0001) primarily decarbonylates furfural to form CO and furan. Similarly, benzaldehyde decarbonylates to benzene with a selectivity that is 7-fold greater over P0.4–Ru(0001) than on Ru(0001). These observations are consistent with weaker interactions between adsorbates and P0.4–Ru(0001) than on Ru(0001) that reflect charge transfer from Ru to P that in turn reduces electron back donation from Ru to the adsorbates and leads to selective decarbonylation of aromatic aldehydes over P0.4–Ru(0001). The distribution of product isotopologues from temperature-programmed reactions of selectively deuterated forms of furfural on P0.4–Ru(0001) shows that furan forms by catalytic transfer hydrogenation (CTH) on P0.4–Ru(0001). The rate-determining step that forms furan from a furanyl surface species involves hydrogen transfer, but H atoms transfer directly from either the aldehydic group or the decomposed aromatic ring of the parent molecule and not from H* atoms chemisorbed to Ru. These findings show that modifying Ru with phosphorus results in the selective rupture of C–C bond required for decarbonylation while facilitating CTH of reactive intermediates from aromatic aldehydes in the absence of an external hydrogen source.

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Section: Resultsmentioning

confidence: 91%

Catalytic Hydrogen Transfer and Decarbonylation of Aromatic Aldehydes on Ru and Ru Phosphide Model Catalysts

2018

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“…On the other hand, benzene has been shown to adsorb by establishing two Si-C bonds with an adatom and a rest atom instead of with a pair of adatoms, because of its reduced size. 3,43,44 As a consequence, we might speculate that TPA molecules adsorbed in the configurations of Fig. 3(a)-(d) might form two monodentate Si-O bonds with Si adatoms in the positions indicated by the corresponding ellipses in Fig.…”

Section: Resultsmentioning

confidence: 99%

Substrate effect on supramolecular self-assembly: from semiconductors to metals

Suzuki

Lutz

Payer

et al. 2009

Phys. Chem. Chem. Phys.

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“…More recently, aromatic hydrocarbons, although smaller than coronene, have been studied on this surface. Benzene is known to adsorb preferentially on the FH [17,18] forming di−σ bonds to an adatom−rest atom pair [19,20,21]. The sticking probability at the center adatoms is twice that at the corner adatoms, since the latter have one adjacent rest atom while the former have two.…”

Section: Resultsmentioning

confidence: 99%

Selective adsorption of coronene on Si(111)-(7×7)

2010

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The adsorption of coronene (C 24 H 12 ) on the Si(111)-(7×7) surface is studied using Scanning Tunneling Microscopy (STM). Upon room temperature submonolayer deposition, we find that the coronene molecules preferentially adsorb on the unfaulted half of the 7×7 unit cell. Molecules adsorbed on different sites can be induced to move to the preferential sites by the action of the tip in repeated image scans. Imaging of the molecules is strongly bias dependent, and also critically depends on the adsorption site. We analyze the results in terms of differential bonding strength for the different adsorption sites and we identify those substrate atoms which participate in the bonding with the molecule.

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Adsorption and desorption of benzene on Si(111)‐7 × 7 studied by scanning tunnelling microscopy

Cited by 26 publications

References 8 publications

Catalytic Hydrogen Transfer and Decarbonylation of Aromatic Aldehydes on Ru and Ru Phosphide Model Catalysts

Catalytic Hydrogen Transfer and Decarbonylation of Aromatic Aldehydes on Ru and Ru Phosphide Model Catalysts

Substrate effect on supramolecular self-assembly: from semiconductors to metals

Selective adsorption of coronene on Si(111)-(7×7)

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