Surface-Templated Assembly of Molecular Methanol on the Thin Film “29” Cu(111) Surface Oxide

Therrien, Andrew J.; Hensley, Alyssa J.  R.; Hannagan, Ryan T.; Schilling, Alex C.; Marcinkowski, Matthew D.; Larson, Amanda M.; McEwen, Jean-Sabin; Sykes, E. Charles H.

doi:10.1021/acs.jpcc.8b10284

Title: Surface-Templated Assembly of Molecular Methanol on the Thin Film “29” Cu(111) Surface Oxide

Full Record
Other Related Research

Abstract

Identifying and characterizing the atomic-scale interaction of methanol with oxidized Cu surfaces is of fundamental relevance to industrial reactions, such as methanol steam reforming and methanol synthesis. Here, we investigate the adsorption of methanol on the well-defined “29” Cu oxide surface, using a combination of experimental and theoretical techniques, and elucidate the atomic-scale interactions that lead to a unique spatial ordering of methanol on the oxide thin film. We determine that the methanol chain structures form first due to epitaxy with the underlying “29” oxide surface. Specifically, the geometry of the “29” oxide is such that there are spatially adjacent O^δ– sites, in the form of O adatoms, and Cu^δ+ species, within the Cu₂O-like rings, which allow for methanol to simultaneously bond to the surface via an O_methanol–Cu^δ+ dative bond and an OH_methanol–O^δ– hydrogen bond. The methanol–oxide bond strength outweighs the strength of methanol–methanol hydrogen bonds on the “29” Cu oxide, unlike methanol assembly on bare coinage metal surfaces on which hydrogen bonding between adjacent molecules leads to ordered arrays. Weak, long-range interactions lead to the formation of chains of only even numbers of methanol molecules. Together, this work reveals that, unlike that on metal surfaces, the corrugation of themore »« less

Authors:

Therrien, Andrew J. ^[1];

^[2]; Hannagan, Ryan T. ^[1]; Schilling, Alex C. ^[1]; Marcinkowski, Matthew D. ^[1]; Larson, Amanda M. ^[1];

^[3];

^[1]

Tufts Univ., Medford, MA (United States)
Washington State Univ., Pullman, WA (United States)
Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Publication Date:: Thu Jan 03 00:00:00 EST 2019

Research Org.:: Tufts Univ., Medford, MA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF)

OSTI Identifier:: 1599612

Grant/Contract Number:: FG02-05ER15730; CBET-1653561

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 123; Journal Issue: 5; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Therrien, Andrew J., Hensley, Alyssa J.  R., Hannagan, Ryan T., Schilling, Alex C., Marcinkowski, Matthew D., Larson, Amanda M., McEwen, Jean-Sabin, and Sykes, E. Charles H. Surface-Templated Assembly of Molecular Methanol on the Thin Film “29” Cu(111) Surface Oxide.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpcc.8b10284.

Copy to clipboard


                    Therrien, Andrew J., Hensley, Alyssa J.  R., Hannagan, Ryan T., Schilling, Alex C., Marcinkowski, Matthew D., Larson, Amanda M., McEwen, Jean-Sabin, & Sykes, E. Charles H. Surface-Templated Assembly of Molecular Methanol on the Thin Film “29” Cu(111) Surface Oxide.  United States.  https://doi.org/10.1021/acs.jpcc.8b10284

Copy to clipboard


                    Therrien, Andrew J., Hensley, Alyssa J.  R., Hannagan, Ryan T., Schilling, Alex C., Marcinkowski, Matthew D., Larson, Amanda M., McEwen, Jean-Sabin, and Sykes, E. Charles H. Thu .  
"Surface-Templated Assembly of Molecular Methanol on the Thin Film “29” Cu(111) Surface Oxide".  United States.  https://doi.org/10.1021/acs.jpcc.8b10284.  https://www.osti.gov/servlets/purl/1599612.

Copy to clipboard


                    
@article{osti_1599612,

  title        = {Surface-Templated Assembly of Molecular Methanol on the Thin Film “29” Cu(111) Surface Oxide},

  author       = {Therrien, Andrew J. and Hensley, Alyssa J.  R. and Hannagan, Ryan T. and Schilling, Alex C. and Marcinkowski, Matthew D. and Larson, Amanda M. and McEwen, Jean-Sabin and Sykes, E. Charles H.},

  abstractNote = {Identifying and characterizing the atomic-scale interaction of methanol with oxidized Cu surfaces is of fundamental relevance to industrial reactions, such as methanol steam reforming and methanol synthesis. Here, we investigate the adsorption of methanol on the well-defined “29” Cu oxide surface, using a combination of experimental and theoretical techniques, and elucidate the atomic-scale interactions that lead to a unique spatial ordering of methanol on the oxide thin film. We determine that the methanol chain structures form first due to epitaxy with the underlying “29” oxide surface. Specifically, the geometry of the “29” oxide is such that there are spatially adjacent Oδ– sites, in the form of O adatoms, and Cuδ+ species, within the Cu2O-like rings, which allow for methanol to simultaneously bond to the surface via an Omethanol–Cuδ+ dative bond and an OHmethanol–Oδ– hydrogen bond. The methanol–oxide bond strength outweighs the strength of methanol–methanol hydrogen bonds on the “29” Cu oxide, unlike methanol assembly on bare coinage metal surfaces on which hydrogen bonding between adjacent molecules leads to ordered arrays. Weak, long-range interactions lead to the formation of chains of only even numbers of methanol molecules. Together, this work reveals that, unlike that on metal surfaces, the corrugation of the oxide surface drives methanol adsorption to preferred binding sites, preventing intermolecular hydrogen bonding and dictating the adsorption geometry.},

  doi          = {10.1021/acs.jpcc.8b10284},

  journal      = {Journal of Physical Chemistry. C},

  number       = 5,

  volume       = 123,

  place        = {United States},

  year         = {Thu Jan 03 00:00:00 EST 2019},

  month        = {Thu Jan 03 00:00:00 EST 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpcc.8b10284

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 7 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Self-assembling of formic acid on the partially oxidized p(2×1) Cu(110) surface reconstruction at low coverages

Journal Article Chen, Zhu ; Martirez, John Mark P. ; Zahl, Percy ; ... - Journal of Chemical Physics

Carbon dioxide (CO₂) reduction for synthetic fuel generation could be an integral part of a sustainable energy future. Copper (Cu) is the leading electrocatalyst for CO₂ reduction to produce multiple C-containing products such as C1 and C2 hydrocarbons and oxygenates. Understanding the mechanisms leading to their production could help optimize these pathways further. Adsorption studies of the many possible intermediates on well-characterized surfaces are crucial to elucidating these mechanisms. In this work, we explore the adsorption configurations of formic acid (HCOOH) on the surface of the partially oxidized p(2 × 1) reconstruction of the Cu(110) surface, using low-temperature scanning tunnelingmore »« less
Cited by 3
https://doi.org/10.1063/1.5046697

Full Text Available
Structure and Chemical State of Cesium on Well-Defined Cu(111) and Cu₂O/Cu(111) Surfaces

Journal Article Hamlyn, Rebecca C. E. ; Mahapatra, Mausumi ; Orozco, Ivan ; ... - Journal of Physical Chemistry. C

The deposition of cesium (Cs) onto the metallic and oxidized surfaces of Cu(111) was investigated using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory calculations (DFT) to elucidate the properties of alkali metals when supported on metal and oxide surfaces. At low coverages, cesium adopts partially cationic (Cs^δ+), highly mobile, and likely atomic structures on the metal surface of Cu(111). Such structures are not observable at room temperature using STM due to rapid surface mobility but can be quantified using XPS. This is further verified by DFT calculations which show that Cs adsorption on Cu(111) ismore »« less
Cited by 12
https://doi.org/10.1021/acs.jpcc.9b10608

Full Text Available
Accelerated Cu₂O Reduction by Single Pt Atoms at the Metal-Oxide Interface

Journal Article Schilling, Alex C. ; Groden, Kyle ; Simonovis, Juan Pablo ; ... - ACS Catalysis

The reducibility of metal oxides, when they serve as the catalyst support or are the active sites themselves, plays an important role in heterogeneous catalytic reactions. Here we present an integrated experimental and theoretical study that reveals how the addition of small amounts of atomically dispersed Pt at the metal/oxide interface dramatically enhances the reducibility of a Cu₂O thin film by H₂. X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) results reveal that, upon oxidation, a PtCu single-atom alloy (SAA) surface is covered by a thin Cu₂O film and is, therefore, unable to dissociate H₂. Despite this, in situ studiesmore »« less
Cited by 22
https://doi.org/10.1021/acscatal.9b05270

Full Text Available
Mechanistic understanding of support effect on the activity and selectivity of indium oxide catalysts for CO₂ hydrogenation

Journal Article Regalado Vera, Clarita Yosune ; Manavi, Narges ; Zhou, Zheng ; ... - Chemical Engineering Journal

Herein we present a mechanistic study on the support effect (ZrO₂ and CeO₂) of In₂O₃ catalysts in CO₂ hydrogenation by a combined experimental and computational approach. Kinetic experiments and surface characterization suggested that the activity of In₂O₃ catalysts cannot be simply correlated with the abundance of surface oxygen vacancies (O_v) formed by either H₂-reduction or thermal treatment, which has been frequently invoked in previous studies. The support effect should originate from the electronic interactions between In₂O₃ and the support oxide, rather than geometric factors or the difference in the particle size of In₂O₃. Theoretical modelling revealed that surface O_v facilitate the formation and stabilization of the formate (HCOO*) intermediate. While a carbonate-like structure is favored for CO₂ adsorption on CeO₂-supported or unsupported In₂O₃ catalysts, CO₂ tends to bind strongly in a bent configuration on the O_v site at the In₂O₃-ZrO₂ interface. The distinct CO₂ adsorption structures on different supported In₂O₃ catalysts may account for the different reaction energy profiles in the subsequent hydrogenation reactions, especially the rate-limiting step, i.e., hydrogenation of HCOO* to CH₂O* and methoxy (CH₃O*). The relatively higher methanol selectivity of In₂O₃ catalyst supported on ZrO₂ with respect to that on CeO₂ are suggested to stem from the greater energy difference (Δmore »« less
https://doi.org/10.1016/j.cej.2021.131767

Full Text Available
Surface science studies of catalyzed methanol synthesis on model copper and Cu-Zn-O surfaces

Miscellaneous Fu, S S

Cu-Zn-O surfaces that are catalysts for methanol synthesis from CO, CO[sub 2], and H[sub 2] are modeled using zinc oxide overlayers on copper single crystals. These studies were performed in ultra-high vacuum (UHV) utilizing Temperature Programmed Desorption, Auger Electron Spectroscopy, and Low Energy Electron Diffraction techniques. The chemisorption of O[sub 2], CO, CO[sub 2], and D[sub 2] were compared on a stepped Cu(311), and a flat Cu(110). At low pressures ([approximately]10[sup [minus]6] Torr), Cu(311) was found to be much more reactive than Cu(110) for the dissociative adsorption of CO[sub 2] and D[sub 2], and the formation of CO[sub 2] frommore »« less

Similar Records