Exploiting basic principles to control the selectivity of the vapor phase catalytic oxidative cross-coupling of primary alcohols over nanoporous gold catalysts

Wang, Lu-Cun; Stowers, Kara J.; Zugic, Branko; Personick, Michelle L.; Biener, Monika M.; Biener, Juergen; Friend, Cynthia M.; Madix, Robert J.

doi:10.1016/j.jcat.2015.04.022

Exploiting basic principles to control the selectivity of the vapor phase catalytic oxidative cross-coupling of primary alcohols over nanoporous gold catalysts

Journal Article · Wed May 20 00:00:00 EDT 2015 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2015.04.022· OSTI ID:1416498

Wang, Lu-Cun ^[1]; Stowers, Kara J. ^[1]; Zugic, Branko ^[1]; Personick, Michelle L. ^[1]; Biener, Monika M. ^[2]; Biener, Juergen ^[2]; Friend, Cynthia M. ^[3]; Madix, Robert J. ^[4]

Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Nanoscale Synthesis and Characterization Lab.
Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology, School of Engineering and Applied Sciences
Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences

It is important to achieve high selectivity for high volume chemical synthesis in order to lower energy consumption through reduction in waste. Here, we report the selective synthesis of methyl esters—methyl acetate and methyl butyrate—through catalytic O₂-assisted cross-coupling of methanol with ethanol or 1-butanol using activated, support-free nanoporous gold (npAu). Both well-controlled studies on ingots in UHV and experiments under ambient pressure catalytic conditions on both ingots and microspherical hollow shell catalysts reveal guiding principles for controlling selectivity. Under UHV conditions, the ester products of the cross-coupling of methanol with both ethanol and 1-butanol evolve near room temperature in temperature-programmed reaction studies, indicating that the reactions occur facilely. Furthermore, under steady-state catalytic operation, high stable activity was observed for cross-coupling in flowing gaseous reactant mixtures at atmospheric pressure and 423 K with negligible combustion. Optimum selectivity for cross-coupling is obtained in methanol-rich mixtures due to a combination of two factors: (1) the relative coverage of the respective alkoxys and (2) the relative facility of their β-H elimination. The relative coverage of the alkoxys is governed by van der Waal’s interactions between the alkyl groups and the surface; here, we demonstrate the importance of these weak interactions in a steady-state catalytic process.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

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

Grant/Contract Number:: AC52-07NA27344; SC0012573

OSTI ID:: 1416498

Alternate ID(s):: OSTI ID: 1210780
OSTI ID: 1252811

Report Number(s):: LLNL-JRNL--737633

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: C Vol. 329; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

Gold Catalysis Hashmi, A. Stephen K.; Hutchings, Graham J. Angewandte Chemie International Edition, Vol. 45, Issue 47 https://doi.org/10.1002/anie.200602454	journal	December 2006
Selectivity Control in Gold-Mediated Esterification of Methanol Xu, Bingjun; Liu, Xiaoying; Haubrich, Jan Angewandte Chemie International Edition, Vol. 48, Issue 23, p. 4206-4209 https://doi.org/10.1002/anie.200805404	journal	May 2009
Oxygen-Mediated Coupling of Alcohols over Nanoporous Gold Catalysts at Ambient Pressures Kosuda, Kathryn M.; Wittstock, Arne; Friend, Cynthia M. Angewandte Chemie International Edition, Vol. 51, Issue 7 https://doi.org/10.1002/anie.201107178	journal	January 2012
On the Role of Residual Ag in Nanoporous Au Catalysts for CO Oxidation: A Combined Microreactor and TAP Reactor Study Wang, L. C.; Zhong, Y.; Widmann, D. ChemCatChem, Vol. 4, Issue 2 https://doi.org/10.1002/cctc.201100297	journal	December 2011
Selective Gas-Phase Oxidation of Alcohols over Nanoporous Silver Li, Zhiwen; Xu, Junling; Gu, Xiaohu ChemCatChem, Vol. 5, Issue 7 https://doi.org/10.1002/cctc.201200862	journal	April 2013
Gold Supported on Nanocrystalline β-Ga ₂ O ₃ as a Versatile Bifunctional Catalyst for Facile Oxidative Transformation of Alcohols, Aldehydes, and Acetals into Esters Su, Fang-Zheng; Ni, Ji; Sun, Hao Chemistry - A European Journal, Vol. 14, Issue 24 https://doi.org/10.1002/chem.200800982	journal	August 2008
Gold Catalysis: In Situ EXAFS Study of Homogeneous Oxidative Esterification Hashmi, A. Stephen K.; Lothschütz, Christian; Ackermann, Martin Chemistry - A European Journal, Vol. 16, Issue 27 https://doi.org/10.1002/chem.200903450	journal	July 2010
Ag/Au Mixed Sites Promote Oxidative Coupling of Methanol on the Alloy Surface Xu, Bingjun; Siler, Cassandra G. F.; Madix, Robert J. Chemistry - A European Journal, Vol. 20, Issue 16 https://doi.org/10.1002/chem.201304837	journal	March 2014
Solvent-free Oxidation of Primary Alcohols to Aldehydes using Supported Gold Catalysts Enache, Dan I.; Knight, David W.; Hutchings, Graham J. Catalysis Letters, Vol. 103, Issue 1-2 https://doi.org/10.1007/s10562-005-6501-y	journal	September 2005
Direct aerobic oxidation of primary alcohols to methyl esters catalyzed by a heterogeneous gold catalyst Nielsen, Inger S.; Taarning, Esben; Egeblad, Kresten Catalysis Letters, Vol. 116, Issue 1-2 https://doi.org/10.1007/s10562-007-9086-9	journal	April 2007
The selective oxidation of CH3OH to H2CO on a copper(110) catalyst Wachs, I. Journal of Catalysis, Vol. 53, Issue 2 https://doi.org/10.1016/0021-9517(78)90068-4	journal	June 1978
The oxidation of methanol on a silver (110) catalyst Wachs, Israel E.; Madix, Robert J. Surface Science, Vol. 76, Issue 2, p. 531-558 https://doi.org/10.1016/0039-6028(78)90113-9	journal	September 1978
The adsorption of molecular oxygen species on Ag(110) Barteau, M. A.; Madix, R. J. Surface Science, Vol. 97, Issue 1 https://doi.org/10.1016/0039-6028(80)90106-5	journal	July 1980
A vibrational study of formic acid interaction with clean and oxygen-covered silver (110) surfaces Sexton, Brett A.; Madix, Robert J. Surface Science, Vol. 105, Issue 1 https://doi.org/10.1016/0039-6028(81)90155-2	journal	April 1981
Atomic and molecular oxygen adsorption on Ag(111) Campbell, Charles T. Surface Science, Vol. 157, Issue 1 https://doi.org/10.1016/0039-6028(85)90634-X	journal	July 1985
Acid-base and nucleophilic chemistry of atomic oxygen on the Au(110) surface: Reactions with formic acid and formaldehyde Outka, Duane A.; Madix, R. J. Surface Science, Vol. 179, Issue 2-3 https://doi.org/10.1016/0039-6028(87)90063-X	journal	January 1987
A HREELS study of C1C5 straight chain alcohols on clean and pre-oxidized Ag(110) surfaces Dai, Qing; Gellman, Andrew J. Surface Science, Vol. 257, Issue 1-3 https://doi.org/10.1016/0039-6028(91)90784-P	journal	November 1991
Scanning tunneling microscopy of oxygen adsorption on the Ag(110) surface Hashizume, Tomihiro; Taniguchi, M.; Motai, K. Surface Science, Vol. 266, Issue 1-3 https://doi.org/10.1016/0039-6028(92)91033-8	journal	April 1992
The oxidation of ethanol on Cu(110) and Ag(110) catalysts Wachs, Israel E.; Madix, Robert J. Applications of Surface Science, Vol. 1, Issue 3 https://doi.org/10.1016/0378-5963(78)90034-X	journal	May 1978
Ethanol dehydrogenation by gold catalysts: The effect of the gold particle size and the presence of oxygen Guan, Yejun; Hensen, Emiel J. M. Applied Catalysis A: General, Vol. 361, Issue 1-2 https://doi.org/10.1016/j.apcata.2009.03.033	journal	June 2009
Aerobic oxidation of benzyl alcohol in methanol solutions over Au nanoparticles: Mg(OH)2 vs MgO as the support Estrada, Miguel; Costa, Vinícius V.; Beloshapkin, Sergey Applied Catalysis A: General, Vol. 473 https://doi.org/10.1016/j.apcata.2013.12.039	journal	March 2014
Dynamic studies of CO oxidation on nanoporous Au using a TAP reactor Wang, L. C.; Jin, H. J.; Widmann, D. Journal of Catalysis, Vol. 278, Issue 2 https://doi.org/10.1016/j.jcat.2010.12.007	journal	March 2011
From model studies on Au(111) to working conditions with unsupported nanoporous gold catalysts: Oxygen-assisted coupling reactions Stowers, K. J.; Madix, R. J.; Friend, C. M. Journal of Catalysis, Vol. 308 https://doi.org/10.1016/j.jcat.2013.05.033	journal	December 2013
CO oxidation on nanoporous gold: A combined TPD and XPS study of active catalysts Röhe, Sarah; Frank, Kristian; Schaefer, Andreas Surface Science, Vol. 609 https://doi.org/10.1016/j.susc.2012.11.011	journal	March 2013
Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts Mallat, Tamas; Baiker, Alfons Chemical Reviews, Vol. 104, Issue 6 https://doi.org/10.1021/cr0200116	journal	June 2004
Heterogeneous Catalysts for the One-Pot Synthesis of Chemicals and Fine Chemicals Climent, Maria J.; Corma, Avelino; Iborra, Sara Chemical Reviews, Vol. 111, Issue 2 https://doi.org/10.1021/cr1002084	journal	February 2011
The .beta.-hydride elimination mechanism in adsorbed alkyl groups Forbes, Jeffrey G.; Gellman, Andrew J. Journal of the American Chemical Society, Vol. 115, Issue 14 https://doi.org/10.1021/ja00067a048	journal	July 1993
Broensted basicity of atomic oxygen on the gold(110) surface: reactions with methanol, acetylene, water, and ethylene Outka, Duane A.; Madix, Robert J. Journal of the American Chemical Society, Vol. 109, Issue 6 https://doi.org/10.1021/ja00240a018	journal	March 1987
Enhancement of O ₂ Dissociation on Au(111) by Adsorbed Oxygen: Implications for Oxidation Catalysis Deng, Xingyi; Min, Byoung Koun; Guloy, Amado Journal of the American Chemical Society, Vol. 127, Issue 25 https://doi.org/10.1021/ja050144j	journal	June 2005
Achieving Optimum Selectivity in Oxygen Assisted Alcohol Cross-Coupling on Gold Xu, Bingjun; Madix, Robert J.; Friend, Cynthia M. Journal of the American Chemical Society, Vol. 132, Issue 46 https://doi.org/10.1021/ja106706v	journal	November 2010
Selective Hydrogen Production from Formic Acid Decomposition on Pd–Au Bimetallic Surfaces Yu, Wen-Yueh; Mullen, Gregory M.; Flaherty, David W. Journal of the American Chemical Society, Vol. 136, Issue 31 https://doi.org/10.1021/ja505192v	journal	July 2014
van der Waals Interactions Determine Selectivity in Catalysis by Metallic Gold Rodriguez-Reyes, Juan Carlos F.; Siler, Cassandra G. F.; Liu, Wei Journal of the American Chemical Society, Vol. 136, Issue 38 https://doi.org/10.1021/ja506447y	journal	September 2014
Surface-Mediated Self-Coupling of Ethanol on Gold Liu, Xiaoying; Xu, Bingjun; Haubrich, Jan Journal of the American Chemical Society, Vol. 131, Issue 16 https://doi.org/10.1021/ja900822r	journal	April 2009
Efficient CO Oxidation at Low Temperature on Au(111) ^† Min, B. K.; Alemozafar, A. R.; Pinnaduwage, D. The Journal of Physical Chemistry B, Vol. 110, Issue 40 https://doi.org/10.1021/jp0616213	journal	October 2006
Toward Controlled Modification of Nanoporous Gold. A Detailed Surface Science Study on Cleaning and Oxidation Schaefer, A.; Ragazzon, D.; Wittstock, A. The Journal of Physical Chemistry C, Vol. 116, Issue 7 https://doi.org/10.1021/jp207638t	journal	February 2012
MnO ₂ Nanorod Supported Gold Nanoparticles with Enhanced Activity for Solvent-free Aerobic Alcohol Oxidation Wang, Lu-Cun; Liu, Yong-Mei; Chen, Miao The Journal of Physical Chemistry C, Vol. 112, Issue 17 https://doi.org/10.1021/jp711333t	journal	May 2008
Atomic Oxygen Adsorption on Au(111) Surfaces with Defects Baker, Thomas A.; Friend, Cynthia M.; Kaxiras, Efthimios The Journal of Physical Chemistry C, Vol. 113, Issue 8 https://doi.org/10.1021/jp806952z	journal	January 2009
Nanoporous Au: An Unsupported Pure Gold Catalyst? Wittstock, Arne; Neumann, Björn; Schaefer, Andreas The Journal of Physical Chemistry C, Vol. 113, Issue 14 https://doi.org/10.1021/jp808185v	journal	March 2009
Nature of Oxidation of the Au(111) Surface: Experimental and Theoretical Investigation Baker, Thomas A.; Xu, Bingjun; Liu, Xiaoying The Journal of Physical Chemistry C, Vol. 113, Issue 38 https://doi.org/10.1021/jp9052192	journal	August 2009
Vapour-phase gold-surface-mediated coupling of aldehydes with methanol Xu, Bingjun; Liu, Xiaoying; Haubrich, Jan Nature Chemistry, Vol. 2, Issue 1 https://doi.org/10.1038/nchem.467	journal	November 2009
Aerobic oxidation of aldehydes under ambient conditions using supported gold nanoparticle catalysts Marsden, Charlotte; Taarning, Esben; Hansen, David Green Chem., Vol. 10, Issue 2 https://doi.org/10.1039/B712171G	journal	January 2008
On the theoretical understanding of the unexpected O ₂ activation by nanoporous gold Fajín, José L. C.; Cordeiro, M. Natália D. S.; Gomes, José R. B. Chem. Commun., Vol. 47, Issue 29 https://doi.org/10.1039/C1CC12166A	journal	January 2011
Methyl ester synthesis catalyzed by nanoporous gold: from 10 ⁻⁹ Torr to 1 atm Wang, Lu-Cun; Stowers, Kara J.; Zugic, Branko Catalysis Science & Technology, Vol. 5, Issue 2 https://doi.org/10.1039/C4CY01169D	journal	January 2015
Silver residues as a possible key to a remarkable oxidative catalytic activity of nanoporous gold Moskaleva, Lyudmila V.; Röhe, Sarah; Wittstock, Arne Physical Chemistry Chemical Physics, Vol. 13, Issue 10 https://doi.org/10.1039/c0cp02372h	journal	January 2011
Oxygen-assisted cross-coupling of methanol with alkyl alcohols on metallic gold Xu, Bingjun; Haubrich, Jan; Freyschlag, Cassandra G. Chemical Science, Vol. 1, Issue 3 https://doi.org/10.1039/c0sc00214c	journal	January 2010
Oxygen-induced restructuring with release of gold atoms from Au(111) Min, B. K.; Deng, X.; Pinnaduwage, D. Physical Review B, Vol. 72, Issue 12 https://doi.org/10.1103/PhysRevB.72.121410	journal	September 2005
Experimental and theoretical study of oxygen adsorption structures on Ag(111) Schnadt, Joachim; Knudsen, Jan; Hu, Xiao Liang Physical Review B, Vol. 80, Issue 7 https://doi.org/10.1103/PhysRevB.80.075424	journal	August 2009
Nanoporous Gold Catalysts for Selective Gas-Phase Oxidative Coupling of Methanol at Low Temperature Wittstock, A.; Zielasek, V.; Biener, J. Science, Vol. 327, Issue 5963 https://doi.org/10.1126/science.1183591	journal	January 2010
Green, Catalytic Oxidation of Alcohols in Water Brink, G. t. Science, Vol. 287, Issue 5458 https://doi.org/10.1126/science.287.5458.1636	journal	March 2000

Cited By (4)

New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica Shirman, Tanya; Lattimer, Judith; Luneau, Mathilde Chemistry - A European Journal, Vol. 24, Issue 8 https://doi.org/10.1002/chem.201704552	journal	November 2017
New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica Shirman, Tanya; Lattimer, Judith; Luneau, Mathilde Chemistry - A European Journal, Vol. 24, Issue 8 https://doi.org/10.1002/chem.201705514	journal	November 2017
Oxygen Adsorption and Low-Temperature CO Oxidation on a Nanoporous Au Catalyst: Reaction Mechanism and Foreign Metal Effects Wang, L. C.; Zhong, Y.; Widmann, D. Topics in Catalysis, Vol. 61, Issue 5-6 https://doi.org/10.1007/s11244-017-0881-2	journal	January 2018
Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts Zugic, Branko; Wang, Lucun; Heine, Christian Nature Materials, Vol. 16, Issue 5 https://doi.org/10.1038/nmat4824	journal	December 2016

Similar Records

Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation

Journal Article · Wed May 27 20:00:00 EDT 2015 · ACS Catalysis · OSTI ID:1413171

Exploiting the Liquid Phase to Enhance the Cross-Coupling of Alcohols over Nanoporous Gold Catalysts

Journal Article · Mon Dec 13 19:00:00 EST 2021 · ACS Catalysis · OSTI ID:1845281

Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity

Journal Article · Mon Feb 01 19:00:00 EST 2016 · ACS Catalysis · OSTI ID:1414356

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Heterogeneous catalysis
Methyl ester synthesis
Nanoporous gold
Oxidation
Reaction mechanism
Selectivity

Exploiting basic principles to control the selectivity of the vapor phase catalytic oxidative cross-coupling of primary alcohols over nanoporous gold catalysts

Citation Formats

References (49)

Cited By (4)

Similar Records

Related Subjects