DFT Study of the Conversion of Furfuryl Alcohol to 2-Methylfuran on RuO2 (110)

Jenness, Glen R.; Vlachos, Dionisios G.

doi:10.1021/jp5109015

DFT Study of the Conversion of Furfuryl Alcohol to 2-Methylfuran on RuO₂ (110)

Journal Article · Wed Feb 18 04:00:00 EST 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp5109015· OSTI ID:1385386

Jenness, Glen R. ^[1]; Vlachos, Dionisios G. ^[1]

Univ. of Delaware, Newark, DE (United States)

Recently, our group proposed the catalytic transfer hydrogenation for refining biomass-derived 5-hydroxymethylfurfural and furfural to 2,5-dimethylfuran and 2-methylfuran, respectively. With a metallic Ru/C catalyst, a selectivity of ~30% was achieved. The promotion of the Ru/C catalyst with the Lewis acid RuO_x resulted in a selectivity of ~80%. In the current study, we employ density functional theory calculations on the RuO₂ (110) surface in order to elucidate the role of the Lewis acidity in the reduction of the biomass-derived furfuryl alcohol to 2-methylfuran. We identify the rate-limiting step to be the scission of the C–O bond of the side chain. In addition, we find evidence for the activation of the furan ring via an insertion of a hydrogen atom. However, the Lewis basicity of a neighboring bridging oxygen results in the furan ring being deactivated. Finally, the formation of water from the reduction process is facile. However, owing to the strong binding energy between the RuO₂ surface and the water molecule, poisoning of the catalytic surface by adsorbed water is possible. Lastly, we show that the RuO₂ (110) carries out the reduction of furfural to furfuryl alcohol via the Meerwin–Ponndorf–Verley (MPV) reaction fairly easily, consistent with published experimental data.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001004; AC02-05CH11231

OSTI ID:: 1385386

Alternate ID(s):: OSTI ID: 1210728

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 11 Vol. 119; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (57)

Der reversible Austausch der Oxydationsstufen zwischen Aldehyden oder Ketonen einerseits und primären oder sekundären Alkoholen anderseits Ponndorf, Wolfgang Zeitschrift für Angewandte Chemie, Vol. 39, Issue 5 https://doi.org/10.1002/ange.19260390504	journal	February 1926
Surface Coordination Chemistry: Dihydrogen versus Hydride Complexes on RuO₂(110) Wang, Jinhai; Fan, Chao Yang; Sun, Qiang Angewandte Chemie, Vol. 115, Issue 19, p. 2201-2204 https://doi.org/10.1002/ange.200250659	journal	May 2003
Hydrogenation of Arenes by Dual Activation: Reduction of Substrates Ranging from Benzene to C ₆₀ Fullerene under Ambient Conditions Deshmukh, Ravindra R.; Lee, Ji Woong; Shin, Ueon Sang Angewandte Chemie International Edition, Vol. 47, Issue 45 https://doi.org/10.1002/anie.200803850	journal	October 2008
The Role of Ru and RuO ₂ in the Catalytic Transfer Hydrogenation of 5-Hydroxymethylfurfural for the Production of 2,5-Dimethylfuran Jae, Jungho; Zheng, Weiqing; Karim, Ayman M. ChemCatChem, Vol. 6, Issue 3 https://doi.org/10.1002/cctc.201300945	journal	February 2014
Furfural-A Promising Platform for Lignocellulosic Biofuels Lange, Jean-Paul; van der Heide, Evert; van Buijtenen, Jeroen ChemSusChem, Vol. 5, Issue 1 https://doi.org/10.1002/cssc.201100648	journal	December 2011
Production of Dimethylfuran from Hydroxymethylfurfural through Catalytic Transfer Hydrogenation with Ruthenium Supported on Carbon Jae, Jungho; Zheng, Weiqing; Lobo, Raul F. ChemSusChem, Vol. 6, Issue 7, p. 1158-1162 https://doi.org/10.1002/cssc.201300288	journal	June 2013
Improved grid-based algorithm for Bader charge allocation Sanville, Edward; Kenny, Steven D.; Smith, Roger Journal of Computational Chemistry, Vol. 28, Issue 5 https://doi.org/10.1002/jcc.20575	journal	January 2007
Ein neues Verfahren zur Reduktion von Aldehyden und Ketonen Meerwein, Hans; Schmidt, Rudolf Justus Liebig's Annalen der Chemie, Vol. 444, Issue 1 https://doi.org/10.1002/jlac.19254440112	journal	January 1925
On the limited memory BFGS method for large scale optimization Liu, Dong C.; Nocedal, Jorge Mathematical Programming, Vol. 45, Issue 1-3 https://doi.org/10.1007/BF01589116	journal	August 1989
Convergence acceleration of iterative sequences. the case of scf iteration Pulay, Péter Chemical Physics Letters, Vol. 73, Issue 2 https://doi.org/10.1016/0009-2614(80)80396-4	journal	July 1980
Electronic factors determining the reactivity of metal surfaces Hammer, B.; Nørskov, J. K. Surface Science, Vol. 343, Issue 3 https://doi.org/10.1016/0039-6028(96)80007-0	journal	December 1995
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Water-resistant solid Lewis acid catalysts: Meerwein–Ponndorf–Verley and Oppenauer reactions catalyzed by tin-beta zeolite Corma, A. Journal of Catalysis, Vol. 215, Issue 2 https://doi.org/10.1016/S0021-9517(03)00014-9	journal	April 2003
Studies in mass spectrometry. Part XXVII. The decomposition of furan, thiophen and deuterated analogues under electron impact Williams, Dudley H.; Graham Cooks, R.; Ronayne, J. Tetrahedron Letters, Vol. 9, Issue 14 https://doi.org/10.1016/S0040-4039(01)99049-5	journal	January 1968
Liquid phase catalytic transfer hydrogenation of furfural over a Ru/C catalyst Panagiotopoulou, Paraskevi; Vlachos, Dionisios G. Applied Catalysis A: General, Vol. 480 https://doi.org/10.1016/j.apcata.2014.04.018	journal	June 2014
Heterogeneous acid-catalysts for the production of furan-derived compounds (furfural and hydroxymethylfurfural) from renewable carbohydrates: A review Agirrezabal-Telleria, I.; Gandarias, I.; Arias, P. L. Catalysis Today, Vol. 234 https://doi.org/10.1016/j.cattod.2013.11.027	journal	October 2014
Kinetics of reduction of a RuO2(110) film on Ru(0001) by atomic hydrogen Ugur, D.; Storm, A. J.; Verberk, R. Microelectronic Engineering, Vol. 110 https://doi.org/10.1016/j.mee.2012.12.031	journal	October 2013
Effect of hydrogen donor on liquid phase catalytic transfer hydrogenation of furfural over a Ru/RuO2/C catalyst Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G. Journal of Molecular Catalysis A: Chemical, Vol. 392 https://doi.org/10.1016/j.molcata.2014.05.016	journal	October 2014
Formation of metastable, heterolytic H-pairs on the RuO2(110) surface Wei, Yinying; Martinez, Umberto; Lammich, Lutz Surface Science, Vol. 619 https://doi.org/10.1016/j.susc.2013.09.020	journal	January 2014
Adsorption and Reaction of Furfural and Furfuryl Alcohol on Pd(111): Unique Reaction Pathways for Multifunctional Reagents Pang, Simon H.; Medlin, J. Will ACS Catalysis, Vol. 1, Issue 10 https://doi.org/10.1021/cs200226h	journal	August 2011
DFT Study of Furfural Conversion to Furan, Furfuryl Alcohol, and 2-Methylfuran on Pd(111) Vorotnikov, Vassili; Mpourmpakis, Giannis; Vlachos, Dionisios G. ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs300395a	journal	October 2012
Brønsted–Evans–Polanyi and Transition State Scaling Relations of Furan Derivatives on Pd(111) and Their Relation to Those of Small Molecules Wang, Shengguang; Vorotnikov, Vassili; Sutton, Jonathan E. ACS Catalysis, Vol. 4, Issue 2 https://doi.org/10.1021/cs400942u	journal	December 2013
Lewis acid catalyzed reactions of methyl propiolate with unactivated alkenes Snider, Barry B.; Rodini, David J.; Conn, Robin S. E. Journal of the American Chemical Society, Vol. 101, Issue 18 https://doi.org/10.1021/ja00512a029	journal	August 1979
Al-Free Sn-Beta Zeolite as a Catalyst for the Selective Reduction of Carbonyl Compounds (Meerwein−Ponndorf−Verley Reaction) Corma, Avelino; Domine, Marcelo E.; Nemeth, Laszlo Journal of the American Chemical Society, Vol. 124, Issue 13, p. 3194-3195 https://doi.org/10.1021/ja012297m	journal	April 2002
The Constitution and Fundamental Properties of Solids and Liquids. part i. Solids. Langmuir, Irving Journal of the American Chemical Society, Vol. 38, Issue 11 https://doi.org/10.1021/ja02268a002	journal	November 1916
Hydrogen Transfer Reaction on the Surface of an Oxide Catalyst Knapp, Marcus; Crihan, Daniela; Seitsonen, Ari P. Journal of the American Chemical Society, Vol. 127, Issue 10 https://doi.org/10.1021/ja043355h	journal	March 2005
Mechanism and Tafel Lines of Electro-Oxidation of Water to Oxygen on RuO ₂ (110) Fang, Ya-Hui; Liu, Zhi-Pan Journal of the American Chemical Society, Vol. 132, Issue 51 https://doi.org/10.1021/ja1069272	journal	December 2010
Identification of Subsurface Oxygen Species Created during Oxidation of Ru(0001) Blume, Raoul; Niehus, Horst; Conrad, Horst The Journal of Physical Chemistry B, Vol. 109, Issue 29 https://doi.org/10.1021/jp044175x	journal	July 2005
Interaction of Hydrogen with RuO ₂ (110) Surfaces: Activity Differences between Various Oxygen Species Jacobi, K.; Wang, Y.; Ertl, G. The Journal of Physical Chemistry B, Vol. 110, Issue 12 https://doi.org/10.1021/jp056341m	journal	March 2006
Unusual Process of Water Formation on RuO ₂ (110) by Hydrogen Exposure at Room Temperature Knapp, M.; Crihan, D.; Seitsonen, A. P. The Journal of Physical Chemistry B, Vol. 110, Issue 29 https://doi.org/10.1021/jp0626622	journal	July 2006
Mechanism of the Meerwein−Ponndorf−Verley−Oppenauer (MPVO) Redox Equilibrium on Sn− and Zr−Beta Zeolite Catalysts Boronat, Mercedes; Corma, Avelino; Renz, Michael The Journal of Physical Chemistry B, Vol. 110, Issue 42 https://doi.org/10.1021/jp063249x	journal	October 2006
Complex Interaction of Hydrogen with the RuO ₂ (110) Surface Knapp, M.; Crihan, D.; Seitsonen, A. P. The Journal of Physical Chemistry C, Vol. 111, Issue 14 https://doi.org/10.1021/jp0667339	journal	March 2007
Homolytic Products from Heterolytic Paths in H ₂ Dissociation on Metal Oxides: The Example of CeO ₂ García-Melchor, Max; López, Núria The Journal of Physical Chemistry C, Vol. 118, Issue 20 https://doi.org/10.1021/jp502309r	journal	May 2014
Role of Lewis Acid(AlCl ₃ )−Aromatic Ring Interactions in Friedel−Craft's Reaction: An ab Initio Study Tarakeshwar, P.; Lee, Jin Yong; Kim, Kwang S. The Journal of Physical Chemistry A, Vol. 102, Issue 13 https://doi.org/10.1021/jp9807322	journal	March 1998
Stereoselective hydrogenation reactions in chloroaluminate(III) ionic liquids: a new method for the reduction of aromatic compounds Adams, Christopher J.; Earle, Martyn J.; Seddon, Kenneth R. Chemical Communications, Issue 11 https://doi.org/10.1039/a901302d	journal	January 1999
A perspective on the modeling of biomass processing Guo, Na; Caratzoulas, Stavros; Doren, Douglas J. Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee02663e	journal	January 2012
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
Comparison of methods for finding saddle points without knowledge of the final states Olsen, R. A.; Kroes, G. J.; Henkelman, G. The Journal of Chemical Physics, Vol. 121, Issue 20 https://doi.org/10.1063/1.1809574	journal	November 2004
Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method Heyden, Andreas; Bell, Alexis T.; Keil, Frerich J. The Journal of Chemical Physics, Vol. 123, Issue 22 https://doi.org/10.1063/1.2104507	journal	December 2005
Superlinearly converging dimer method for transition state search Kästner, Johannes; Sherwood, Paul The Journal of Chemical Physics, Vol. 128, Issue 1 https://doi.org/10.1063/1.2815812	journal	January 2008
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 111, Issue 15 https://doi.org/10.1063/1.480097	journal	October 1999
A new method for diagonalising large matrices Wood, D. M.; Zunger, A. Journal of Physics A: Mathematical and General, Vol. 18, Issue 9 https://doi.org/10.1088/0305-4470/18/9/018	journal	June 1985
Electronic structure of RuO 2 , OsO 2 , and IrO 2 Mattheiss, L. F. Physical Review B, Vol. 13, Issue 6 https://doi.org/10.1103/PhysRevB.13.2433	journal	March 1976
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Self-consistent band structure of the rutile dioxides NbO2, RuO2, and IrO2 Xu, J.; Jarlborg, T.; Freeman, A. Physical Review B, Vol. 40, Issue 11 https://doi.org/10.1103/PhysRevB.40.7939	journal	October 1989
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
A chemical and theoretical way to look at bonding on surfaces Hoffmann, Roald Reviews of Modern Physics, Vol. 60, Issue 3 https://doi.org/10.1103/RevModPhys.60.601	journal	July 1988
Structural Studies of Rutile-Type Metal Dioxides Bolzan, A. A.; Fong, C.; Kennedy, B. J. Acta Crystallographica Section B Structural Science, Vol. 53, Issue 3 https://doi.org/10.1107/S0108768197001468	journal	June 1997
Rutile-type compounds. IV. SiO2, GeO2 and a comparison with other rutile-type structures Baur, W. H.; Khan, A. A. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 27, Issue 11 https://doi.org/10.1107/S0567740871005466	journal	November 1971
An object-oriented scripting interface to a legacy electronic structure code Bahn, S. R.; Jacobsen, K. W. Computing in Science & Engineering, Vol. 4, Issue 3 https://doi.org/10.1109/5992.998641	journal	January 2002
Selective Phenol Hydrogenation to Cyclohexanone Over a Dual Supported Pd–Lewis Acid Catalyst Liu, Huizhen; Jiang, Tao; Han, Buxing Science, Vol. 326, Issue 5957 https://doi.org/10.1126/science.1179713	journal	November 2009
Atomic-Scale Structure and Catalytic Reactivity of the RuO2(110) Surface Over, H. Science, Vol. 287, Issue 5457 https://doi.org/10.1126/science.287.5457.1474	journal	February 2000

Cited By (4)

Metal Catalysts for the Efficient Transformation of Biomass-derived HMF and Furfural to Value Added Chemicals Gupta, Kavita; Rai, Rohit K.; Singh, Sanjay K. ChemCatChem, Vol. 10, Issue 11 https://doi.org/10.1002/cctc.201701754	journal	March 2018
Selective Deoxygenation of Biomass-Derived Bio-oils within Hydrogen-Modest Environments: A Review and New Insights Rogers, Kyle A.; Zheng, Ying ChemSusChem, Vol. 9, Issue 14 https://doi.org/10.1002/cssc.201600144	journal	July 2016
DFT investigation on the adsorption of munition compounds on α-Fe ₂ O ₃ : similarity and differences with α-Al ₂ O ₃ Jenness, Glen R.; Seiter, Jennifer; Shukla, Manoj K. Physical Chemistry Chemical Physics, Vol. 20, Issue 27 https://doi.org/10.1039/c8cp02590h	journal	January 2018
Catalytic conversion of 5-hydroxymethylfurfural to some value-added derivatives Kong, Xiao; Zhu, Yifeng; Fang, Zhen Green Chemistry, Vol. 20, Issue 16 https://doi.org/10.1039/c8gc00234g	journal	January 2018

Similar Records

A comparative study of thermal- and electrocatalytic conversion of furfural: methylfuran as a primary and major product

Journal Article · Wed Apr 29 00:00:00 EDT 2020 · Journal of Applied Electrochemistry · OSTI ID:1775274

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
alcohols
aldehydes binding energy
bio-inspired
biofuels (including algae and biomass)
catalysis (heterogeneous)
catalysis (homogeneous)
chemical reactions
hydrogen
hydrogen and fuel cells
materials and chemistry by design
synthesis (novel materials)
synthesis (scalable processing)
synthesis (self-assembly)