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Title: Methanol Oxidation to Formaldehyde Promoted at the Step Sites of Ultrathin ZnO

Abstract

Adsorption and oxidation of methanol on ultrathin ZnO layers supported on Au(111) have been investigated using temperature programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. In the TPRS experiments, following adsorption of methanol-18O at T = 100 K, only molecular methanol-18O desorbed from the planar ZnO bilayer surface at T = 220 and 260 K, whereas a partial oxidation product, formaldehyde-18O (~95% selectivity), and a small amount of carbon dioxide (C16O18O) were produced at T = 580 K at the bilayer–trilayer step sites. The DFT calculations were used to identify the adsorption configurations of methanol on the planar ZnO surface and at the step sites, as well as the reaction pathways to gaseous formaldehyde. The most stable adsorption configuration corresponds to methanol molecule adsorbed at the bilayer–trilayer step sites with its C–O axis parallel to the upper terrace edge, forming a bond between its O atom and a Zn site on the lower terrace, and also a hydrogen bond between its H atom in the OH group and a lattice O anion at the upper terrace edge. Starting from the most stable adsorption configuration at the step sites, formation of gaseous formaldehyde was found to take place preferentiallymore » via a methoxy (CH3O(ad)) intermediate. This process follows the pathways CH3OH(ad) → CH3O(ad) + H(ad) → CH2O(g) + 2H(ad) and has an overall barrier of 19.0 kcal/mol. The reaction pathway to produce a lattice O-bonded formaldehyde (H2COOlattice(ad)), the proposed precursor leading to CO2, was found to be energetically less favorable with a barrier of ~38 kcal/mol. As a result, the preference to produce gaseous formaldehyde from the DFT calculations agrees well with the high selectivity toward formaldehyde observed in the TPRS experiments.« less

Authors:
 [1];  [2];  [1]
  1. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); AECOM, South Park, PA (United States)
  2. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
Publication Date:
Research Org.:
National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States). In-house Research
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1478389
Alternate Identifier(s):
OSTI ID: 1491096
Report Number(s):
CONTR-PUB-327
Journal ID: ISSN 1022-5528; PII: 867
Grant/Contract Number:  
FE0004000
Resource Type:
Accepted Manuscript
Journal Name:
Topics in Catalysis
Additional Journal Information:
Journal Volume: 61; Journal Issue: 5-6; Journal ID: ISSN 1022-5528
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Methanol oxidation; Formaldehyde; Ultrathin ZnO; Temperature programmed reaction spectroscopy; Density functional theory; Minimum energy pathway

Citation Formats

Deng, Xingyi, Sorescu, Dan C., and Lee, Junseok. Methanol Oxidation to Formaldehyde Promoted at the Step Sites of Ultrathin ZnO. United States: N. p., 2018. Web. doi:10.1007/s11244-017-0867-0.
Deng, Xingyi, Sorescu, Dan C., & Lee, Junseok. Methanol Oxidation to Formaldehyde Promoted at the Step Sites of Ultrathin ZnO. United States. doi:10.1007/s11244-017-0867-0.
Deng, Xingyi, Sorescu, Dan C., and Lee, Junseok. Mon . "Methanol Oxidation to Formaldehyde Promoted at the Step Sites of Ultrathin ZnO". United States. doi:10.1007/s11244-017-0867-0. https://www.osti.gov/servlets/purl/1478389.
@article{osti_1478389,
title = {Methanol Oxidation to Formaldehyde Promoted at the Step Sites of Ultrathin ZnO},
author = {Deng, Xingyi and Sorescu, Dan C. and Lee, Junseok},
abstractNote = {Adsorption and oxidation of methanol on ultrathin ZnO layers supported on Au(111) have been investigated using temperature programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. In the TPRS experiments, following adsorption of methanol-18O at T = 100 K, only molecular methanol-18O desorbed from the planar ZnO bilayer surface at T = 220 and 260 K, whereas a partial oxidation product, formaldehyde-18O (~95% selectivity), and a small amount of carbon dioxide (C16O18O) were produced at T = 580 K at the bilayer–trilayer step sites. The DFT calculations were used to identify the adsorption configurations of methanol on the planar ZnO surface and at the step sites, as well as the reaction pathways to gaseous formaldehyde. The most stable adsorption configuration corresponds to methanol molecule adsorbed at the bilayer–trilayer step sites with its C–O axis parallel to the upper terrace edge, forming a bond between its O atom and a Zn site on the lower terrace, and also a hydrogen bond between its H atom in the OH group and a lattice O anion at the upper terrace edge. Starting from the most stable adsorption configuration at the step sites, formation of gaseous formaldehyde was found to take place preferentially via a methoxy (CH3O(ad)) intermediate. This process follows the pathways CH3OH(ad) → CH3O(ad) + H(ad) → CH2O(g) + 2H(ad) and has an overall barrier of 19.0 kcal/mol. The reaction pathway to produce a lattice O-bonded formaldehyde (H2COOlattice(ad)), the proposed precursor leading to CO2, was found to be energetically less favorable with a barrier of ~38 kcal/mol. As a result, the preference to produce gaseous formaldehyde from the DFT calculations agrees well with the high selectivity toward formaldehyde observed in the TPRS experiments.},
doi = {10.1007/s11244-017-0867-0},
journal = {Topics in Catalysis},
number = 5-6,
volume = 61,
place = {United States},
year = {2018},
month = {3}
}

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    Works referencing / citing this record:

    Synergic and Antifouling Effect of ZnO on Ethanol Oxidation by Silver-Palladium Bimetallic Electrocatalyst
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