The role of water in the adsorption of oxygenated aromatics on Pt and Pd

Jin Yang, Paul J. Dauenhauer, Ashwin Ramasubramaniam

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Catalytic processing of biomass-derived oxygenates to valuable chemical products will contribute to a sustainable future. To provide insight into the conversion of processed sugars and lignin monomers, we present density functional theory studies of adsorption of phloroglucinol, a potentially valuable biomass derivative, on Pt(111) and Pd(111) surfaces. A comprehensive study of adsorption geometries and associated energies indicates that the bridge site is the most preferred adsorption site for phloroglucinol, with binding energies in the range of 2-3 eV in the vapor phase. Adsorption of phloroglucinol on these metal surfaces occurs via hybridization between the carbon p z orbitals and the metal d z 2 and dyz orbitals. With explicit solvent, hydrogen bonds are formed between phloroglucinol and water molecules thereby decreasing binding of phloroglucinol to the metal surfaces relative to the vapor phase by 20-25%. Based on these results, we conclude that solvent effects can significantly impact adsorption of oxygenated aromatic compounds derived from biomass and influence catalytic hydrogenation and hydrodeoxygenation reactions as well.

Original languageEnglish (US)
Pages (from-to)60-66
Number of pages7
JournalJournal of Computational Chemistry
Volume34
Issue number1
DOIs
StatePublished - Jan 5 2013

Fingerprint

Phloroglucinol
Adsorption
Water
Biomass
Metals
Vapors
Solvent Effect
Hydrogen Bonds
Aromatic compounds
Lignin
Binding Energy
Sugars
Binding energy
Density Functional
Hydrogenation
Density functional theory
Hydrogen bonds
Carbon
Monomers
Molecules

Keywords

  • catalysis
  • density functional theory
  • green chemistry
  • surface chemistry

Cite this

The role of water in the adsorption of oxygenated aromatics on Pt and Pd. / Yang, Jin; Dauenhauer, Paul J.; Ramasubramaniam, Ashwin.

In: Journal of Computational Chemistry, Vol. 34, No. 1, 05.01.2013, p. 60-66.

Research output: Contribution to journalArticle

@article{167b4d70acdc458ebe287c3c97a1adf7,
title = "The role of water in the adsorption of oxygenated aromatics on Pt and Pd",
abstract = "Catalytic processing of biomass-derived oxygenates to valuable chemical products will contribute to a sustainable future. To provide insight into the conversion of processed sugars and lignin monomers, we present density functional theory studies of adsorption of phloroglucinol, a potentially valuable biomass derivative, on Pt(111) and Pd(111) surfaces. A comprehensive study of adsorption geometries and associated energies indicates that the bridge site is the most preferred adsorption site for phloroglucinol, with binding energies in the range of 2-3 eV in the vapor phase. Adsorption of phloroglucinol on these metal surfaces occurs via hybridization between the carbon p z orbitals and the metal d z 2 and dyz orbitals. With explicit solvent, hydrogen bonds are formed between phloroglucinol and water molecules thereby decreasing binding of phloroglucinol to the metal surfaces relative to the vapor phase by 20-25{\%}. Based on these results, we conclude that solvent effects can significantly impact adsorption of oxygenated aromatic compounds derived from biomass and influence catalytic hydrogenation and hydrodeoxygenation reactions as well.",
keywords = "catalysis, density functional theory, green chemistry, surface chemistry",
author = "Jin Yang and Dauenhauer, {Paul J.} and Ashwin Ramasubramaniam",
year = "2013",
month = "1",
day = "5",
doi = "10.1002/jcc.23107",
language = "English (US)",
volume = "34",
pages = "60--66",
journal = "Journal of Computational Chemistry",
issn = "0192-8651",
publisher = "John Wiley and Sons Inc.",
number = "1",

}

TY - JOUR

T1 - The role of water in the adsorption of oxygenated aromatics on Pt and Pd

AU - Yang, Jin

AU - Dauenhauer, Paul J.

AU - Ramasubramaniam, Ashwin

PY - 2013/1/5

Y1 - 2013/1/5

N2 - Catalytic processing of biomass-derived oxygenates to valuable chemical products will contribute to a sustainable future. To provide insight into the conversion of processed sugars and lignin monomers, we present density functional theory studies of adsorption of phloroglucinol, a potentially valuable biomass derivative, on Pt(111) and Pd(111) surfaces. A comprehensive study of adsorption geometries and associated energies indicates that the bridge site is the most preferred adsorption site for phloroglucinol, with binding energies in the range of 2-3 eV in the vapor phase. Adsorption of phloroglucinol on these metal surfaces occurs via hybridization between the carbon p z orbitals and the metal d z 2 and dyz orbitals. With explicit solvent, hydrogen bonds are formed between phloroglucinol and water molecules thereby decreasing binding of phloroglucinol to the metal surfaces relative to the vapor phase by 20-25%. Based on these results, we conclude that solvent effects can significantly impact adsorption of oxygenated aromatic compounds derived from biomass and influence catalytic hydrogenation and hydrodeoxygenation reactions as well.

AB - Catalytic processing of biomass-derived oxygenates to valuable chemical products will contribute to a sustainable future. To provide insight into the conversion of processed sugars and lignin monomers, we present density functional theory studies of adsorption of phloroglucinol, a potentially valuable biomass derivative, on Pt(111) and Pd(111) surfaces. A comprehensive study of adsorption geometries and associated energies indicates that the bridge site is the most preferred adsorption site for phloroglucinol, with binding energies in the range of 2-3 eV in the vapor phase. Adsorption of phloroglucinol on these metal surfaces occurs via hybridization between the carbon p z orbitals and the metal d z 2 and dyz orbitals. With explicit solvent, hydrogen bonds are formed between phloroglucinol and water molecules thereby decreasing binding of phloroglucinol to the metal surfaces relative to the vapor phase by 20-25%. Based on these results, we conclude that solvent effects can significantly impact adsorption of oxygenated aromatic compounds derived from biomass and influence catalytic hydrogenation and hydrodeoxygenation reactions as well.

KW - catalysis

KW - density functional theory

KW - green chemistry

KW - surface chemistry

UR - http://www.scopus.com/inward/record.url?scp=84870053730&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84870053730&partnerID=8YFLogxK

U2 - 10.1002/jcc.23107

DO - 10.1002/jcc.23107

M3 - Article

C2 - 22941861

AN - SCOPUS:84870053730

VL - 34

SP - 60

EP - 66

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

SN - 0192-8651

IS - 1

ER -