skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Coverage-Induced Conformational Effects on Activity and Selectivity: Hydrogenation and Decarbonylation of Furfural on Pd(111)

Abstract

Adsorption, hydrogenation, and decarbonylation of furfural on hydrogen-covered Pd(111) was investigated using density functional theory calculations. It was found that both the energy and the conformation of adsorbed furfural vary with increasing coverage of hydrogen or furfural. Furfural lies flat at low coverage but becomes tilted on crowded surfaces. The energy profiles of hydrogenation and decarbonylation reactions on a hydrogen-covered Pd(111) change profoundly compared to those on bare Pd(111). The energy span theory shows that the furfural hydrogenation and decarbonylation effective barriers exhibit a maximum with increasing hydrogen coverage. In contrast, the selectivity to hydrogenation toward furfuryl alcohol over decarbonylation is favored with increasing hydrogen coverage. Microkinetic modeling suggests that the conformation change with increasing H coverage has a significant effect on reaction rates (up to orders of magnitude) and induces a selectivity reversal from furan as the main product (low-H coverage limit) to furfuryl alcohol (high-H coverage limit). Our results may rationalize different selectivity trends seen experimentally under typical reactor and UHV conditions. Importantly, this study underscores the potential importance of operating conditions on hydrodeoxygenation activity and selectivity due to conformational changes of multifunctional biomass derivatives.

Authors:
 [1];  [1];  [1]
  1. Department of Chemical and Biomolecular Engineering, Catalysis Center for Energy Innovation, and Center for Catalytic Science and Technology, University of Delaware, Newark, Delaware 19716, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1246455
Alternate Identifier(s):
OSTI ID: 1385128
Grant/Contract Number:  
SC0001004; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Name: ACS Catalysis Journal Volume: 5 Journal Issue: 1; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); biofuels (including algae and biomass); bio-inspired; hydrogen and fuel cells; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing); furfural; furfuryl alcohol; furan; Pd; hydrogenation; decarbonylation; coverage effects; conformation effect; Hydrogen; Aldehydes; Adsorption; Conformation

Citation Formats

Wang, Shengguang, Vorotnikov, Vassili, and Vlachos, Dionisios G. Coverage-Induced Conformational Effects on Activity and Selectivity: Hydrogenation and Decarbonylation of Furfural on Pd(111). United States: N. p., 2014. Web. https://doi.org/10.1021/cs5015145.
Wang, Shengguang, Vorotnikov, Vassili, & Vlachos, Dionisios G. Coverage-Induced Conformational Effects on Activity and Selectivity: Hydrogenation and Decarbonylation of Furfural on Pd(111). United States. https://doi.org/10.1021/cs5015145
Wang, Shengguang, Vorotnikov, Vassili, and Vlachos, Dionisios G. Tue . "Coverage-Induced Conformational Effects on Activity and Selectivity: Hydrogenation and Decarbonylation of Furfural on Pd(111)". United States. https://doi.org/10.1021/cs5015145.
@article{osti_1246455,
title = {Coverage-Induced Conformational Effects on Activity and Selectivity: Hydrogenation and Decarbonylation of Furfural on Pd(111)},
author = {Wang, Shengguang and Vorotnikov, Vassili and Vlachos, Dionisios G.},
abstractNote = {Adsorption, hydrogenation, and decarbonylation of furfural on hydrogen-covered Pd(111) was investigated using density functional theory calculations. It was found that both the energy and the conformation of adsorbed furfural vary with increasing coverage of hydrogen or furfural. Furfural lies flat at low coverage but becomes tilted on crowded surfaces. The energy profiles of hydrogenation and decarbonylation reactions on a hydrogen-covered Pd(111) change profoundly compared to those on bare Pd(111). The energy span theory shows that the furfural hydrogenation and decarbonylation effective barriers exhibit a maximum with increasing hydrogen coverage. In contrast, the selectivity to hydrogenation toward furfuryl alcohol over decarbonylation is favored with increasing hydrogen coverage. Microkinetic modeling suggests that the conformation change with increasing H coverage has a significant effect on reaction rates (up to orders of magnitude) and induces a selectivity reversal from furan as the main product (low-H coverage limit) to furfuryl alcohol (high-H coverage limit). Our results may rationalize different selectivity trends seen experimentally under typical reactor and UHV conditions. Importantly, this study underscores the potential importance of operating conditions on hydrodeoxygenation activity and selectivity due to conformational changes of multifunctional biomass derivatives.},
doi = {10.1021/cs5015145},
journal = {ACS Catalysis},
number = 1,
volume = 5,
place = {United States},
year = {2014},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/cs5015145

Citation Metrics:
Cited by: 37 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Kinetics and mechanism of hydrogenation of furfural on Cu/SiO2 catalysts
journal, January 2011


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Interplay between carbon monoxide, hydrides, and carbides in selective alkyne hydrogenation on palladium
journal, July 2010

  • García-Mota, Mónica; Bridier, Blaise; Pérez-Ramírez, Javier
  • Journal of Catalysis, Vol. 273, Issue 2
  • DOI: 10.1016/j.jcat.2010.04.018

DFT Study of Furfural Conversion to Furan, Furfuryl Alcohol, and 2-Methylfuran on Pd(111)
journal, October 2012

  • Vorotnikov, Vassili; Mpourmpakis, Giannis; Vlachos, Dionisios G.
  • ACS Catalysis, Vol. 2, Issue 12
  • DOI: 10.1021/cs300395a

Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals
journal, February 2010


Projector augmented-wave method
journal, December 1994


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Group Additivity for Estimating Thermochemical Properties of Furanic Compounds on Pd(111)
journal, July 2014

  • Vorotnikov, Vassili; Wang, Shengguang; Vlachos, Dionisios G.
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 30
  • DOI: 10.1021/ie502049a

A DFT study of furan hydrogenation and ring opening on Pd(111)
journal, January 2014

  • Wang, Shengguang; Vorotnikov, Vassili; Vlachos, Dionisios G.
  • Green Chem., Vol. 16, Issue 2
  • DOI: 10.1039/c3gc41183d

Effect of multiscale model uncertainty on identification of optimal catalyst properties
journal, July 2011


Hydrodeoxygenation of Furfural Over Supported Metal Catalysts: A Comparative Study of Cu, Pd and Ni
journal, March 2011


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

How to Conceptualize Catalytic Cycles? The Energetic Span Model
journal, February 2011

  • Kozuch, Sebastian; Shaik, Sason
  • Accounts of Chemical Research, Vol. 44, Issue 2
  • DOI: 10.1021/ar1000956

Kinetic Modeling of Pt Catalyzed and Computation-Driven Catalyst Discovery for Ethylene Glycol Decomposition
journal, August 2011

  • Salciccioli, M.; Vlachos, D. G.
  • ACS Catalysis, Vol. 1, Issue 10
  • DOI: 10.1021/cs2003593

In silico search for novel methane steam reforming catalysts
journal, December 2013


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Hydrogenation of carbonylic compounds
journal, January 2000


Catalytic Conversion of Renewable Biomass Resources to Fuels and Chemicals
journal, June 2010


Conversion of furfural and 2-methylpentanal on Pd/SiO2 and Pd–Cu/SiO2 catalysts
journal, May 2011


Brønsted–Evans–Polanyi and Transition State Scaling Relations of Furan Derivatives on Pd(111) and Their Relation to Those of Small Molecules
journal, December 2013

  • Wang, Shengguang; Vorotnikov, Vassili; Sutton, Jonathan E.
  • ACS Catalysis, Vol. 4, Issue 2
  • DOI: 10.1021/cs400942u

A Generalized Approach for Predicting Coverage-Dependent Reaction Parameters of Complex Surface Reactions:  Application to H 2 Oxidation over Platinum
journal, October 1999

  • Park, Young K.; Aghalayam, Preeti; Vlachos, Dionisios G.
  • The Journal of Physical Chemistry A, Vol. 103, Issue 40
  • DOI: 10.1021/jp9916485

A refinement of everyday thinking: the energetic span model for kinetic assessment of catalytic cycles: Energetic span, a refinement of everyday thinking
journal, April 2012

  • Kozuch, Sebastian
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 5
  • DOI: 10.1002/wcms.1100

Liquid phase hydrogenation of furfural to furfuryl alcohol over the Fe-promoted Ni-B amorphous alloy catalysts
journal, September 2003


Ultra-selective cycloaddition of dimethylfuran for renewable p-xylene with H-BEA
journal, January 2014

  • Chang, Chun-Chih; Green, Sara K.; Williams, C. Luke
  • Green Chem., Vol. 16, Issue 2
  • DOI: 10.1039/c3gc40740c

Silica supported transition metal-based bimetallic catalysts for vapour phase selective hydrogenation of furfuraldehyde
journal, March 2007

  • Reddy, Benjaram M.; Reddy, Gunugunuri K.; Rao, Komateedi N.
  • Journal of Molecular Catalysis A: Chemical, Vol. 265, Issue 1-2
  • DOI: 10.1016/j.molcata.2006.10.034

Size dependence of the lattice parameter of small palladium particles
journal, April 1995


Preparation and catalysis of amorphous CoNiB and polymer-stabilized CoNiB catalysts for hydrogenation of unsaturated aldehydes
journal, August 2008


Selective conversion of furfural to methylfuran over silica-supported NiFe bimetallic catalysts
journal, November 2011


Platinum deposited on monolayer supports in selective hydrogenation of furfural to furfuryl alcohol
journal, July 2002


Surface-level mechanistic studies of adsorbate–adsorbate interactions in heterogeneous catalysis by metals
journal, May 2011


Combined DFT, Microkinetic, and Experimental Study of Ethanol Steam Reforming on Pt
journal, February 2013

  • Sutton, Jonathan E.; Panagiotopoulou, Paraskevi; Verykios, Xenophon E.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 9
  • DOI: 10.1021/jp312593u

A review of multiscale modeling of metal-catalyzed reactions: Mechanism development for complexity and emergent behavior
journal, October 2011

  • Salciccioli, M.; Stamatakis, M.; Caratzoulas, S.
  • Chemical Engineering Science, Vol. 66, Issue 19
  • DOI: 10.1016/j.ces.2011.05.050

Hydrogenation of furfural over copper-containing catalysts
journal, February 1981


Properties of Copper Chromite Catalysts in Hydrogenation Reactions
journal, October 1997


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Directing reaction pathways by catalyst active-site selection using self-assembled monolayers
journal, September 2013

  • Pang, Simon H.; Schoenbaum, Carolyn A.; Schwartz, Daniel K.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3448

Understanding and Controlling Reactivity of Unsaturated Oxygenates and Polyols on Metal Catalysts
journal, August 2011


Surface Chemistry of 2-Iodoethanol on Pd(111): Orientation of Surface-Bound Alcohol Controls Selectivity
journal, February 2012

  • Griffin, Michael B.; Pang, Simon H.; Medlin, J. Will
  • The Journal of Physical Chemistry C, Vol. 116, Issue 6
  • DOI: 10.1021/jp211259h

Improved tetrahedron method for Brillouin-zone integrations
journal, June 1994


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344