Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110)
Abstract
The relative stability of carboxylates on Au(110) was investigated as part of a comprehensive study of adsorbate binding on Group IB metals that can be used to predict and understand how to control reactivity in heterogeneous catalysis. The binding efficacy of carboxylates is only weakly dependent on alkyl chain length for relatively short-chain molecules, as demonstrated using quantitative temperature-programmed reaction spectroscopy. Corresponding density functional theory (DFT) calculations demonstrated that the bidentate anchoring geometry is rigid and restricts the amount of additional stabilization through adsorbate-surface van der Waals (vdW) interactions which control stability for alkoxides. A combination of scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) shows that carboxylates form dense local islands on Au(110). Complementary DFT calculations demonstrate that adsorbate–adsorbate interactions provide additional stabilization that increases as a function of alkyl chain length for C2 and C3 carboxylates. Hence, overall stability is generally a function of the anchoring group to the surface and the inter-adsorbate interaction. This study demonstrates the importance of these two important factors in describing binding of key catalytic intermediates.
- Authors:
-
- Department of Chemistry and Chemical Biology, Harvard University, Cambridge, USA
- School of Engineering and Applied Sciences, Harvard University, Cambridge, USA, Department of Physics
- School of Engineering and Applied Sciences, Harvard University, Cambridge, USA
- Department of Chemistry and Chemical Biology, Harvard University, Cambridge, USA, School of Engineering and Applied Sciences
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1430376
- Alternate Identifier(s):
- OSTI ID: 1470273
- Grant/Contract Number:
- SC0012573
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 15; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); mesostructured materials; materials and chemistry by design; synthesis (novel materials)
Citation Formats
O'Connor, Christopher R., Hiebel, Fanny, Chen, Wei, Kaxiras, Efthimios, Madix, Robert J., and Friend, Cynthia M. Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110). United Kingdom: N. p., 2018.
Web. doi:10.1039/C7SC05313D.
O'Connor, Christopher R., Hiebel, Fanny, Chen, Wei, Kaxiras, Efthimios, Madix, Robert J., & Friend, Cynthia M. Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110). United Kingdom. https://doi.org/10.1039/C7SC05313D
O'Connor, Christopher R., Hiebel, Fanny, Chen, Wei, Kaxiras, Efthimios, Madix, Robert J., and Friend, Cynthia M. Mon .
"Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110)". United Kingdom. https://doi.org/10.1039/C7SC05313D.
@article{osti_1430376,
title = {Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110)},
author = {O'Connor, Christopher R. and Hiebel, Fanny and Chen, Wei and Kaxiras, Efthimios and Madix, Robert J. and Friend, Cynthia M.},
abstractNote = {The relative stability of carboxylates on Au(110) was investigated as part of a comprehensive study of adsorbate binding on Group IB metals that can be used to predict and understand how to control reactivity in heterogeneous catalysis. The binding efficacy of carboxylates is only weakly dependent on alkyl chain length for relatively short-chain molecules, as demonstrated using quantitative temperature-programmed reaction spectroscopy. Corresponding density functional theory (DFT) calculations demonstrated that the bidentate anchoring geometry is rigid and restricts the amount of additional stabilization through adsorbate-surface van der Waals (vdW) interactions which control stability for alkoxides. A combination of scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) shows that carboxylates form dense local islands on Au(110). Complementary DFT calculations demonstrate that adsorbate–adsorbate interactions provide additional stabilization that increases as a function of alkyl chain length for C2 and C3 carboxylates. Hence, overall stability is generally a function of the anchoring group to the surface and the inter-adsorbate interaction. This study demonstrates the importance of these two important factors in describing binding of key catalytic intermediates.},
doi = {10.1039/C7SC05313D},
journal = {Chemical Science},
number = 15,
volume = 9,
place = {United Kingdom},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}
https://doi.org/10.1039/C7SC05313D
Web of Science
Figures / Tables:
Works referenced in this record:
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
Tuning the Stability of Surface Intermediates Using Adsorbed Oxygen: Acetate on Au(111)
journal, March 2014
- Cremer, Till; Siler, Cassandra G. F.; Rodríguez-Reyes, Juan Carlos F.
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 7
The Materials Super Highway: Integrating High-Throughput Experimentation into Mapping the Catalysis Materials Genome
journal, November 2014
- Hattrick-Simpers, Jason; Wen, Cun; Lauterbach, Jochen
- Catalysis Letters, Vol. 145, Issue 1
A combined STM/molecular beam study of formic acid oxidation on Cu(110)
journal, May 1998
- Bowker, Michael; Poulston, Stephen; Bennett, Roger A.
- Journal of Molecular Catalysis A: Chemical, Vol. 131, Issue 1-3
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
A van der Waals DFT study of chain length dependence of alkanethiol adsorption on Au(111): physisorption vs. chemisorption
journal, January 2017
- Mete, Ersen; Yortanlı, Merve; Danışman, Mehmet Fatih
- Physical Chemistry Chemical Physics, Vol. 19, Issue 21
Perspective on Materials Genome®
journal, January 2014
- Liu, Zikui
- Chinese Science Bulletin, Vol. 59, Issue 15
Exploring the Possibilities and Limitations of a Nanomaterials Genome
journal, September 2014
- Qian, Chenxi; Siler, Todd; Ozin, Geoffrey A.
- Small, Vol. 11, Issue 1
Promoting gold nanocatalysts in solvent-free selective aerobic oxidation of alcohols
journal, January 2007
- Zheng, Nanfeng; Stucky, Galen D.
- Chemical Communications, Issue 37
Acetic acid adsorption and decomposition on Pd(110)
journal, April 2004
- Bowker, Michael; Morgan, Chris; Couves, John
- Surface Science, Vol. 555, Issue 1-3
Surface acidity scales: Experimental measurements of Brønsted acidities on anatase TiO2 and comparison with coinage metal surfaces
journal, August 2016
- Silbaugh, Trent L.; Boaventura, Jaime S.; Barteau, Mark A.
- Surface Science, Vol. 650
General Effect of van der Waals Interactions on the Stability of Alkoxy Intermediates on Metal Surfaces
journal, August 2017
- Xu, Yunfei; Chen, Wei; Kaxiras, Efthimios
- The Journal of Physical Chemistry B, Vol. 122, Issue 2
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Surface-Mediated Self-Coupling of Ethanol on Gold
journal, April 2009
- Liu, Xiaoying; Xu, Bingjun; Haubrich, Jan
- Journal of the American Chemical Society, Vol. 131, Issue 16
Structural comparison of self-assembled monolayers of n-alkanoic acids on the surfaces of silver, copper, and aluminum
journal, May 1993
- Tao, Yu Tai
- Journal of the American Chemical Society, Vol. 115, Issue 10
Epoxidation of olefins with molecular oxygen as the oxidant using gold catalysts supported on polyoxometalates
journal, January 2014
- Tebandeke, Emmanuel; Coman, Cristina; Guillois, Kevin
- Green Chemistry, Vol. 16, Issue 3
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009
- Tkatchenko, Alexandre; Scheffler, Matthias
- Physical Review Letters, Vol. 102, Issue 7
A study of the relative brönsted acidities of surface complexes on Ag(110)
journal, August 1982
- Barteau, M. A.; Madix, R. J.
- Surface Science, Vol. 120, Issue 2
Utilisation of CO2 as a chemical feedstock: opportunities and challenges
journal, January 2007
- Aresta, Michele; Dibenedetto, Angela
- Dalton Transactions, Issue 28
Selectivity Control in Gold-Mediated Esterification of Methanol
journal, May 2009
- Xu, Bingjun; Liu, Xiaoying; Haubrich, Jan
- Angewandte Chemie International Edition, Vol. 48, Issue 23, p. 4206-4209
The Entropies of Adsorbed Molecules
journal, October 2012
- Campbell, Charles T.; Sellers, Jason R. V.
- Journal of the American Chemical Society, Vol. 134, Issue 43
The Role of Surface Deconstruction in the Autocatalytic Decomposition of Formate and Acetate on Ni(110) †
journal, September 2004
- Alemozafar, Ali R.; Madix, Robert J.
- The Journal of Physical Chemistry B, Vol. 108, Issue 38
Basic Research Needs: Catalysis for Energy
report, March 2008
- Bell, Alexis T.; Gates, Bruce C.; Ray, Douglas
- PNNL--17214
The Activation of Gold and the Water–Gas Shift Reaction: Insights from Studies with Model Catalysts
journal, November 2013
- Rodriguez, José A.; Senanayake, Sanjaya D.; Stacchiola, Dario
- Accounts of Chemical Research, Vol. 47, Issue 3
Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes
journal, June 2017
- Feaster, Jeremy T.; Shi, Chuan; Cave, Etosha R.
- ACS Catalysis, Vol. 7, Issue 7
Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol
journal, October 2016
- Karakalos, Stavros; Zugic, Branko; Stowers, Kara J.
- Surface Science, Vol. 652
STM study of d-alanine adsorption on Cu(001)
journal, January 2005
- Iwai, Hidekazu; Tobisawa, Mine; Emori, Akira
- Surface Science, Vol. 574, Issue 2-3
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
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
The Materials Genome Initiative, the interplay of experiment, theory and computation
journal, April 2014
- de Pablo, Juan J.; Jones, Barbara; Kovacs, Cora Lind
- Current Opinion in Solid State and Materials Science, Vol. 18, Issue 2
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
The Role of Gold in Gold-Titania Epoxidation Catalysts
journal, February 2005
- Nijhuis, T. Alexander; Visser, Tom; Weckhuysen, Bert M.
- Angewandte Chemie International Edition, Vol. 44, Issue 7
The oxidation of carbon monoxide on the Au(110) surface
journal, January 1987
- Outka, Duane A.; Madix, R. J.
- Surface Science, Vol. 179, Issue 2-3
Long-range periodicity in c(8 × 2) benzoate/Cu(110): a combined STM, LEED and HREELS study
journal, December 1997
- Frederick, B. G.; Chen, Q.; Leibsle, F. M.
- Surface Science, Vol. 394, Issue 1-3
Dynamics of adsorption and phase formation of p-nitrobenzoic acid at Au(111) surface in solution: A combined surface-enhanced infrared and STM study
journal, January 2001
- Noda, Hiroyuki; Wan, Li-Jun; Osawa, Masatoshi
- Physical Chemistry Chemical Physics, Vol. 3, Issue 16
Oxygen chemisorption on Au()-(1×2) I. Thermal desorption measurements
journal, February 2003
- Gottfried, J. M.; Schmidt, K. J.; Schroeder, S. L. M.
- Surface Science, Vol. 525, Issue 1-3
Electrochemical Reduction of CO 2 at Functionalized Au Electrodes
journal, February 2017
- Fang, Yuxin; Flake, John C.
- Journal of the American Chemical Society, Vol. 139, Issue 9
Photocatalytic oxidation of cyclohexane by titanium dioxide: Catalyst deactivation and regeneration
journal, July 2010
- Carneiro, Joana T.; Moulijn, Jacob A.; Mul, Guido
- Journal of Catalysis, Vol. 273, Issue 2
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Microscopic View of the Active Sites for Selective Dehydrogenation of Formic Acid on Cu(111)
journal, November 2015
- Marcinkowski, Matthew D.; Murphy, Colin J.; Liriano, Melissa L.
- ACS Catalysis, Vol. 5, Issue 12
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013
- Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
- APL Materials, Vol. 1, Issue 1
Noncovalent Bonding Controls Selectivity in Heterogeneous Catalysis: Coupling Reactions on Gold
journal, November 2016
- Karakalos, Stavros; Xu, Yunfei; Cheenicode Kabeer, Fairoja
- Journal of the American Chemical Society, Vol. 138, Issue 46
The Catalyst Genome
journal, December 2012
- Nørskov, Jens K.; Bligaard, Thomas
- Angewandte Chemie International Edition, Vol. 52, Issue 3
First-Principles Study of Alkoxides Adsorbed on Au(111) and Au(110) Surfaces: Assessing the Roles of Noncovalent Interactions and Molecular Structures in Catalysis
journal, December 2017
- Cheenicode Kabeer, Fairoja; Chen, Wei; Madix, Robert J.
- The Journal of Physical Chemistry C, Vol. 121, Issue 50
X-RAY PHOTOELECTRON DIFFRACTION STUDY OF A LONG-RANGE-ORDERED ACETATE LAYER ON Ni(110)
journal, February 2000
- Nowicki, M.; Emundts, A.; Werner, J.
- Surface Review and Letters, Vol. 07, Issue 01n02
Research Update: The materials genome initiative: Data sharing and the impact of collaborative ab initio databases
journal, March 2016
- Jain, Anubhav; Persson, Kristin A.; Ceder, Gerbrand
- APL Materials, Vol. 4, Issue 5
Fulfilling the promise of the materials genome initiative with high-throughput experimental methodologies
journal, March 2017
- Green, M. L.; Choi, C. L.; Hattrick-Simpers, J. R.
- Applied Physics Reviews, Vol. 4, Issue 1
Computational Evidence for Lewis Base-Promoted CO 2 Hydrogenation to Formic Acid on Gold Surfaces
journal, June 2017
- Lv, Xiangying; Lu, Gang; Wang, Zhi-Qiao
- ACS Catalysis, Vol. 7, Issue 7
Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Au-Pd/TiO 2 Catalysts
journal, January 2006
- Enache, Dan I.; Edwards, Jennifer K.; Landon, Philip
- Science, Vol. 311, Issue 5759
Gold catalysts for pure hydrogen production in the water–gas shift reaction: activity, structure and reaction mechanism
journal, January 2006
- Burch, Robbie
- Phys. Chem. Chem. Phys., Vol. 8, Issue 47
Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface
journal, October 2016
- Hiebel, Fanny; Shong, Bonggeun; Chen, Wei
- Nature Communications, Vol. 7, Issue 1
Selectivity control during the photoassisted oxidation of 1-butanol on titanium dioxide
journal, October 1988
- Blake, N. R.; Griffin, G. L.
- The Journal of Physical Chemistry, Vol. 92, Issue 20
Styrene Epoxidation over Carbon Nanotube-Supported Gold Catalysts
journal, November 2009
- Liu, Junhua; Wang, Fang; Xu, Tan
- Catalysis Letters, Vol. 134, Issue 1-2
Switching Selectivity in Oxidation Reactions on Gold: The Mechanism of C–C vs C–H Bond Activation in the Acetate Intermediate on Au(111)
journal, August 2014
- Siler, Cassandra G. F.; Cremer, Till; Rodriguez-Reyes, Juan Carlos F.
- ACS Catalysis, Vol. 4, Issue 9
Oxidation of Styrene and Phenylacetaldehyde on Ag(111): Evidence for Transformation of Surface Oxametallacycle
journal, March 2008
- Zhou, Ling; Madix, Robert J.
- The Journal of Physical Chemistry C, Vol. 112, Issue 12
Broensted basicity of atomic oxygen on the gold(110) surface: reactions with methanol, acetylene, water, and ethylene
journal, March 1987
- Outka, Duane A.; Madix, Robert J.
- Journal of the American Chemical Society, Vol. 109, Issue 6
Formation and decomposition of acetate intermediates on the Ag(110) surface
journal, January 1981
- Barteau, M.
- Journal of Catalysis, Vol. 67, Issue 1
The relative acidities of gas phase acids for displacement of surface intermediates
journal, July 1983
- Jorgensen, Scott W.; Madix, R. J.
- Surface Science, Vol. 130, Issue 1
Selective Vapor-Phase Epoxidation of Propylene over Au/TiO2Catalysts in the Presence of Oxygen and Hydrogen
journal, September 1998
- Hayashi, Toshio; Tanaka, Koji; Haruta, Masatake
- Journal of Catalysis, Vol. 178, Issue 2
STM, FTIR and quantum chemical calculation studies of acetate structures on Cu() surfaces
journal, January 2003
- York, S. M.; Haq, S.; Kilway, K. V.
- Surface Science, Vol. 522, Issue 1-3
First-Principles Based Kinetic Simulations of Acetic Acid Temperature Programmed Reaction on Pd(111)
journal, September 2001
- Hansen, Eric; Neurock, Matthew
- The Journal of Physical Chemistry B, Vol. 105, Issue 38
The Role of Gold in Gold-Titania Epoxidation Catalysts
journal, February 2005
- Nijhuis, T. Alexander; Visser, Tom; Weckhuysen, Bert M.
- Angewandte Chemie, Vol. 117, Issue 7
Works referencing / citing this record:
Oxygen-assisted stabilization of single-atom Au during photocatalytic hydrogen evolution
journal, January 2019
- Zeng, Lei; Dai, Chunhui; Liu, Bin
- Journal of Materials Chemistry A, Vol. 7, Issue 42
Figures / Tables found in this record: