l-Arabinose Conformers Adsorption on Ruthenium Surfaces: A DFT Study

Remedios Cortese, Dario Duca, Dmitry Yu. Murzin, Victor Alberto Sifontes Herrera

Risultato della ricerca: Article

9 Citazioni (Scopus)

Abstract

Adsorption of 5 L-arabinose tautomers – one acyclic and four cyclic (α and β, pyranose and furanose) species – on a ruthenium surface was studied as a precursor-process of the, nowadays more and more, industrially important sugar catalytic hydrogenation on metal surfaces in water medium. The study was mostly referred to a 37-atom metal catalyst fragment, even though border-effects on the adsorption processes were also checked employing a 61-atom metal fragment. In order to figure out conformational effects on the title process the tautomer flexibility was, at first, investigated by the genetic-algorithm based code Balloon, considering the conformational spaces of the different aquo tautomers. On the whole, 30 L-arabinose conformers, representing the complete conformational set (of a “realistic” water solution), were isolated by the genetic-algorithm based code Balloon. These were further refined at DFT level and then analyzed when interacting with a ruthenium surface, always at DFT level, by SIESTA. It was found that i) cyclic L-arabinose tautomers give rise to less strong adsorption than the acyclic tautomeric form; ii) L-arabinose molecules preferentially adsorb perpendicularly to the metallic surface; iii) one among the α-pyranose and one among the β-furanose derivatives are largely the most abundant adsorbed species; iv) the dominant L-arabinopyranose andL-arabinofuranose surface configurations are clearly related to corresponding not-adsorbed species that preserve both conformations and intramolecular hydrogen bonds during their the adsorption. The consideration of the points above allowed us to pick out significant properties, characterizing L-arabinose adsorption on ruthenium.
Lingua originaleEnglish
pagine (da-a)14908-14916
Numero di pagine9
RivistaJOURNAL OF PHYSICAL CHEMISTRY. C
Volume116
Stato di pubblicazionePublished - 2012

Fingerprint

Arabinose
Ruthenium
Discrete Fourier transforms
ruthenium
tautomers
Adsorption
adsorption
Metals
Balloons
balloons
genetic algorithms
Genetic algorithms
fragments
Atoms
Water
sugars
borders
Sugars
metals
water

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cita questo

l-Arabinose Conformers Adsorption on Ruthenium Surfaces: A DFT Study. / Cortese, Remedios; Duca, Dario; Murzin, Dmitry Yu.; Sifontes Herrera, Victor Alberto.

In: JOURNAL OF PHYSICAL CHEMISTRY. C, Vol. 116, 2012, pag. 14908-14916.

Risultato della ricerca: Article

Cortese, Remedios ; Duca, Dario ; Murzin, Dmitry Yu. ; Sifontes Herrera, Victor Alberto. / l-Arabinose Conformers Adsorption on Ruthenium Surfaces: A DFT Study. In: JOURNAL OF PHYSICAL CHEMISTRY. C. 2012 ; Vol. 116. pagg. 14908-14916.
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abstract = "Adsorption of 5 L-arabinose tautomers – one acyclic and four cyclic (α and β, pyranose and furanose) species – on a ruthenium surface was studied as a precursor-process of the, nowadays more and more, industrially important sugar catalytic hydrogenation on metal surfaces in water medium. The study was mostly referred to a 37-atom metal catalyst fragment, even though border-effects on the adsorption processes were also checked employing a 61-atom metal fragment. In order to figure out conformational effects on the title process the tautomer flexibility was, at first, investigated by the genetic-algorithm based code Balloon, considering the conformational spaces of the different aquo tautomers. On the whole, 30 L-arabinose conformers, representing the complete conformational set (of a “realistic” water solution), were isolated by the genetic-algorithm based code Balloon. These were further refined at DFT level and then analyzed when interacting with a ruthenium surface, always at DFT level, by SIESTA. It was found that i) cyclic L-arabinose tautomers give rise to less strong adsorption than the acyclic tautomeric form; ii) L-arabinose molecules preferentially adsorb perpendicularly to the metallic surface; iii) one among the α-pyranose and one among the β-furanose derivatives are largely the most abundant adsorbed species; iv) the dominant L-arabinopyranose andL-arabinofuranose surface configurations are clearly related to corresponding not-adsorbed species that preserve both conformations and intramolecular hydrogen bonds during their the adsorption. The consideration of the points above allowed us to pick out significant properties, characterizing L-arabinose adsorption on ruthenium.",
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N2 - Adsorption of 5 L-arabinose tautomers – one acyclic and four cyclic (α and β, pyranose and furanose) species – on a ruthenium surface was studied as a precursor-process of the, nowadays more and more, industrially important sugar catalytic hydrogenation on metal surfaces in water medium. The study was mostly referred to a 37-atom metal catalyst fragment, even though border-effects on the adsorption processes were also checked employing a 61-atom metal fragment. In order to figure out conformational effects on the title process the tautomer flexibility was, at first, investigated by the genetic-algorithm based code Balloon, considering the conformational spaces of the different aquo tautomers. On the whole, 30 L-arabinose conformers, representing the complete conformational set (of a “realistic” water solution), were isolated by the genetic-algorithm based code Balloon. These were further refined at DFT level and then analyzed when interacting with a ruthenium surface, always at DFT level, by SIESTA. It was found that i) cyclic L-arabinose tautomers give rise to less strong adsorption than the acyclic tautomeric form; ii) L-arabinose molecules preferentially adsorb perpendicularly to the metallic surface; iii) one among the α-pyranose and one among the β-furanose derivatives are largely the most abundant adsorbed species; iv) the dominant L-arabinopyranose andL-arabinofuranose surface configurations are clearly related to corresponding not-adsorbed species that preserve both conformations and intramolecular hydrogen bonds during their the adsorption. The consideration of the points above allowed us to pick out significant properties, characterizing L-arabinose adsorption on ruthenium.

AB - Adsorption of 5 L-arabinose tautomers – one acyclic and four cyclic (α and β, pyranose and furanose) species – on a ruthenium surface was studied as a precursor-process of the, nowadays more and more, industrially important sugar catalytic hydrogenation on metal surfaces in water medium. The study was mostly referred to a 37-atom metal catalyst fragment, even though border-effects on the adsorption processes were also checked employing a 61-atom metal fragment. In order to figure out conformational effects on the title process the tautomer flexibility was, at first, investigated by the genetic-algorithm based code Balloon, considering the conformational spaces of the different aquo tautomers. On the whole, 30 L-arabinose conformers, representing the complete conformational set (of a “realistic” water solution), were isolated by the genetic-algorithm based code Balloon. These were further refined at DFT level and then analyzed when interacting with a ruthenium surface, always at DFT level, by SIESTA. It was found that i) cyclic L-arabinose tautomers give rise to less strong adsorption than the acyclic tautomeric form; ii) L-arabinose molecules preferentially adsorb perpendicularly to the metallic surface; iii) one among the α-pyranose and one among the β-furanose derivatives are largely the most abundant adsorbed species; iv) the dominant L-arabinopyranose andL-arabinofuranose surface configurations are clearly related to corresponding not-adsorbed species that preserve both conformations and intramolecular hydrogen bonds during their the adsorption. The consideration of the points above allowed us to pick out significant properties, characterizing L-arabinose adsorption on ruthenium.

KW - DFT studies

KW - adsorption energies

KW - conformational analysis

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KW - ruthenium catalysts

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