Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity
Abstract
We demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. These results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order to achieve comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shownmore »
- Authors:
-
- 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). School of Engineering and Applied Sciences
- Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology, School of Engineering and Applied Sciences
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1414356
- Report Number(s):
- LLNL-JRNL-737635
Journal ID: ISSN 2155-5435; TRN: US1800688
- Grant/Contract Number:
- AC52-07NA27344; SC0012573
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 3; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; esterification; green catalysis; methyl acrylate; methyl methacrylate; nanoporous gold; selective alcohol oxidation
Citation Formats
Zugic, Branko, Karakalos, Stavros, Stowers, Kara J., Biener, Monika M., Biener, Juergen, Madix, Robert J., and Friend, Cynthia M. Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity. United States: N. p., 2016.
Web. doi:10.1021/acscatal.5b02902.
Zugic, Branko, Karakalos, Stavros, Stowers, Kara J., Biener, Monika M., Biener, Juergen, Madix, Robert J., & Friend, Cynthia M. Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity. United States. https://doi.org/10.1021/acscatal.5b02902
Zugic, Branko, Karakalos, Stavros, Stowers, Kara J., Biener, Monika M., Biener, Juergen, Madix, Robert J., and Friend, Cynthia M. Tue .
"Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity". United States. https://doi.org/10.1021/acscatal.5b02902. https://www.osti.gov/servlets/purl/1414356.
@article{osti_1414356,
title = {Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity},
author = {Zugic, Branko and Karakalos, Stavros and Stowers, Kara J. and Biener, Monika M. and Biener, Juergen and Madix, Robert J. and Friend, Cynthia M.},
abstractNote = {We demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. These results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order to achieve comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shown to be a good qualitative indicator for the relative binding strength of the alkoxides. This work then provides insight into the control of reaction selectivity for coupling reactions and demonstrates the value of fundamental studies on single crystals for establishing key principles governing reaction selectivity. Notably, these oxygen-assisted coupling reactions occur without oxidation of the C=C bond.},
doi = {10.1021/acscatal.5b02902},
journal = {ACS Catalysis},
number = 3,
volume = 6,
place = {United States},
year = {Tue Feb 02 00:00:00 EST 2016},
month = {Tue Feb 02 00:00:00 EST 2016}
}
Web of Science
Works referenced in this record:
Pd–Pb/SDB Bimetallic Catalysts for The Direct Oxidative Esterification of Methacrolein to Methyl Methacrylate
journal, November 2012
- Wang, Baohe; Sun, Wenjuan; Zhu, Jing
- Industrial & Engineering Chemistry Research, Vol. 51, Issue 46
Aerobic Oxidative Esterification of Aldehydes with Alcohols by Gold–Nickel Oxide Nanoparticle Catalysts with a Core–Shell Structure
journal, July 2013
- Suzuki, Ken; Yamaguchi, Tatsuo; Matsushita, Ken
- ACS Catalysis, Vol. 3, Issue 8
Direct aerobic oxidation of primary alcohols to methyl esters catalyzed by a heterogeneous gold catalyst
journal, April 2007
- Nielsen, Inger S.; Taarning, Esben; Egeblad, Kresten
- Catalysis Letters, Vol. 116, Issue 1-2
Gold-Catalyzed Carbon−Heteroatom Bond-Forming Reactions
journal, March 2011
- Corma, A.; Leyva-Pérez, A.; Sabater, Maria J.
- Chemical Reviews, Vol. 111, Issue 3
Vapour-phase gold-surface-mediated coupling of aldehydes with methanol
journal, November 2009
- Xu, Bingjun; Liu, Xiaoying; Haubrich, Jan
- Nature Chemistry, Vol. 2, Issue 1
Converting carbohydrates to bulk chemicals and fine chemicals over heterogeneous catalysts
journal, January 2011
- Climent, Maria J.; Corma, Avelino; Iborra, Sara
- Green Chemistry, Vol. 13, Issue 3
Gold nanoparticle catalysts for selective hydrogenations
journal, January 2013
- Mitsudome, Takato; Kaneda, Kiyotomi
- Green Chemistry, Vol. 15, Issue 10
Solvent-free Oxidation of Primary Alcohols to Aldehydes using Supported Gold Catalysts
journal, September 2005
- Enache, Dan I.; Knight, David W.; Hutchings, Graham J.
- Catalysis Letters, Vol. 103, Issue 1-2
A review of the use of gold catalysts in selective hydrogenation reactions Lynsey McEwana
journal, December 2010
- Juliusa, Melissa; Robertsa, Stephen; Fletchera, Jack C. Q.
- Gold Bulletin, Vol. 43, Issue 4
Oxygen-assisted cross-coupling of methanol with alkyl alcohols on metallic gold
journal, January 2010
- Xu, Bingjun; Haubrich, Jan; Freyschlag, Cassandra G.
- Chemical Science, Vol. 1, Issue 3
Partial Oxidation of Propene on Oxygen-Covered Au(111)
journal, August 2006
- Deng, Xingyi; Min, Byoung Koun; Liu, Xiaoying
- The Journal of Physical Chemistry B, Vol. 110, Issue 32
Oxygen and Hydroxyl Species Induce Multiple Reaction Pathways for the Partial Oxidation of Allyl Alcohol on Gold
journal, April 2014
- Mullen, Gregory M.; Zhang, Liang; Evans, Edward J.
- Journal of the American Chemical Society, Vol. 136, Issue 17
Control of selectivity in allylic alcohol oxidation on gold surfaces: the role of oxygen adatoms and hydroxyl species
journal, January 2015
- Mullen, Gregory M.; Zhang, Liang; Evans, Edward J.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 6
Exploiting basic principles to control the selectivity of the vapor phase catalytic oxidative cross-coupling of primary alcohols over nanoporous gold catalysts
journal, September 2015
- Wang, Lu-Cun; Stowers, Kara J.; Zugic, Branko
- Journal of Catalysis, Vol. 329
Catalysis by Supported Gold Nanoparticles: Beyond Aerobic Oxidative Processes
journal, May 2012
- Stratakis, Manolis; Garcia, Hermenegildo
- Chemical Reviews, Vol. 112, Issue 8
Gold-Based Nanoparticulate Catalysts for the Oxidative Esterification of 1,4-Butanediol to Dimethyl Succinate
journal, November 2013
- Brett, Gemma L.; Miedziak, Peter J.; Knight, David W.
- Topics in Catalysis, Vol. 57, Issue 6-9
Oxidative Esterification of Homologous 1,3-Propanediols
journal, July 2012
- Kotionova, Tatyana; Lee, Christopher; Miedziak, Peter J.
- Catalysis Letters, Vol. 142, Issue 9
Methyl ester synthesis catalyzed by nanoporous gold: from 10 −9 Torr to 1 atm
journal, January 2015
- Wang, Lu-Cun; Stowers, Kara J.; Zugic, Branko
- Catalysis Science & Technology, Vol. 5, Issue 2
Achieving Optimum Selectivity in Oxygen Assisted Alcohol Cross-Coupling on Gold
journal, November 2010
- Xu, Bingjun; Madix, Robert J.; Friend, Cynthia M.
- Journal of the American Chemical Society, Vol. 132, Issue 46
van der Waals Interactions Determine Selectivity in Catalysis by Metallic Gold
journal, September 2014
- Rodriguez-Reyes, Juan Carlos F.; Siler, Cassandra G. F.; Liu, Wei
- Journal of the American Chemical Society, Vol. 136, Issue 38
Nanoporous Gold Leaf: ?Ancient Technology?/Advanced Material
journal, November 2004
- Ding, Y.; Kim, Y. -J.; Erlebacher, J.
- Advanced Materials, Vol. 16, Issue 21
Nanoporous Gold Catalysts for Selective Gas-Phase Oxidative Coupling of Methanol at Low Temperature
journal, January 2010
- Wittstock, A.; Zielasek, V.; Biener, J.
- Science, Vol. 327, Issue 5963
From model studies on Au(111) to working conditions with unsupported nanoporous gold catalysts: Oxygen-assisted coupling reactions
journal, December 2013
- Stowers, K. J.; Madix, R. J.; Friend, C. M.
- Journal of Catalysis, Vol. 308
Toward Controlled Modification of Nanoporous Gold. A Detailed Surface Science Study on Cleaning and Oxidation
journal, February 2012
- Schaefer, A.; Ragazzon, D.; Wittstock, A.
- The Journal of Physical Chemistry C, Vol. 116, Issue 7
Enhancement of O 2 Dissociation on Au(111) by Adsorbed Oxygen: Implications for Oxidation Catalysis
journal, June 2005
- Deng, Xingyi; Min, Byoung Koun; Guloy, Amado
- Journal of the American Chemical Society, Vol. 127, Issue 25
Origin of the selectivity in the gold-mediated oxidation of benzyl alcohol
journal, August 2012
- Rodríguez-Reyes, Juan Carlos F.; Friend, Cynthia M.; Madix, Robert J.
- Surface Science, Vol. 606, Issue 15-16
Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation
journal, June 2015
- Personick, Michelle L.; Zugic, Branko; Biener, Monika M.
- ACS Catalysis, Vol. 5, Issue 7
Works referencing / citing this record:
New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica
journal, November 2017
- Shirman, Tanya; Lattimer, Judith; Luneau, Mathilde
- Chemistry - A European Journal, Vol. 24, Issue 8
Nanoporous gold functionalized with praseodymia–titania mixed oxides as a stable catalyst for the water–gas shift reaction
journal, January 2019
- Shi, Junjie; Wittstock, Arne; Mahr, Christoph
- Physical Chemistry Chemical Physics, Vol. 21, Issue 6
New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica
journal, November 2017
- Shirman, Tanya; Lattimer, Judith; Luneau, Mathilde
- Chemistry - A European Journal, Vol. 24, Issue 8