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Title: Combining Theory and Experiment for Multitechnique Characterization of Activated CO 2 on Transition Metal Carbide (001) Surfaces

Early transition metal carbides (TMC; TM = Ti, Zr, Hf, V, Nb, Ta, Mo) with face-centered cubic crystallographic structure have emerged as promising materials for CO 2 capture and activation. Density functional theory (DFT) calculations using the Perdew–Burke–Ernzerhof exchange–correlation functional evidence charge transfer from the TMC surface to CO 2 on the two possible adsorption sites, namely, MMC and TopC, and the electronic structure and binding strength differences are discussed. Further, the suitability of multiple experimental techniques with respect to (1) adsorbed CO2 recognition and (2) MMC/TopC adsorption distinction is assessed from extensive DFT simulations. Results show that ultraviolet photoemission spectroscopies (UPS), work function changes, core level X-ray photoemission spectroscopy (XPS), and changes in linear optical properties could well allow for adsorbed CO2 detection. Only infrared (IR) spectra and scanning tunnelling microscopy (STM) seem to additionally allow for MMC/TopC adsorption site distinction. These findings are confirmed with experimental XPS measurements, demonstrating CO 2 binding on single crystal (001) surfaces of TiC, ZrC, and VC. The experiments also help resolving ambiguities for VC, where CO 2 activation was unexpected due to low adsorption energy, but could be related to kinetic trapping involving a desorption barrier. With a wealth of data reportedmore » and direct experimental evidence provided, this study aims to motivate further basic surface science experiments on an interesting case of CO 2 activating materials, allowing also for a benchmark of employed theoretical models.« less
Authors:
 [1] ; ORCiD logo [1] ;  [2] ; ORCiD logo [3] ; ORCiD logo [1]
  1. Univ. of Barcelona (Spain)
  2. Univ. Central de Venezuela, Caracas (Venezuela)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Report Number(s):
BNL-200037-2018-JAAM
Journal ID: ISSN 1932-7447; TRN: US1802010
Grant/Contract Number:
SC0012704
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. C; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1425041

Kunkel, Christian, Viñes, Francesc, Ramírez, Pedro J., Rodriguez, Jose A., and Illas, Francesc. Combining Theory and Experiment for Multitechnique Characterization of Activated CO2 on Transition Metal Carbide (001) Surfaces. United States: N. p., Web. doi:10.1021/acs.jpcc.7b12227.
Kunkel, Christian, Viñes, Francesc, Ramírez, Pedro J., Rodriguez, Jose A., & Illas, Francesc. Combining Theory and Experiment for Multitechnique Characterization of Activated CO2 on Transition Metal Carbide (001) Surfaces. United States. doi:10.1021/acs.jpcc.7b12227.
Kunkel, Christian, Viñes, Francesc, Ramírez, Pedro J., Rodriguez, Jose A., and Illas, Francesc. 2018. "Combining Theory and Experiment for Multitechnique Characterization of Activated CO2 on Transition Metal Carbide (001) Surfaces". United States. doi:10.1021/acs.jpcc.7b12227.
@article{osti_1425041,
title = {Combining Theory and Experiment for Multitechnique Characterization of Activated CO2 on Transition Metal Carbide (001) Surfaces},
author = {Kunkel, Christian and Viñes, Francesc and Ramírez, Pedro J. and Rodriguez, Jose A. and Illas, Francesc},
abstractNote = {Early transition metal carbides (TMC; TM = Ti, Zr, Hf, V, Nb, Ta, Mo) with face-centered cubic crystallographic structure have emerged as promising materials for CO2 capture and activation. Density functional theory (DFT) calculations using the Perdew–Burke–Ernzerhof exchange–correlation functional evidence charge transfer from the TMC surface to CO2 on the two possible adsorption sites, namely, MMC and TopC, and the electronic structure and binding strength differences are discussed. Further, the suitability of multiple experimental techniques with respect to (1) adsorbed CO2 recognition and (2) MMC/TopC adsorption distinction is assessed from extensive DFT simulations. Results show that ultraviolet photoemission spectroscopies (UPS), work function changes, core level X-ray photoemission spectroscopy (XPS), and changes in linear optical properties could well allow for adsorbed CO2 detection. Only infrared (IR) spectra and scanning tunnelling microscopy (STM) seem to additionally allow for MMC/TopC adsorption site distinction. These findings are confirmed with experimental XPS measurements, demonstrating CO2 binding on single crystal (001) surfaces of TiC, ZrC, and VC. The experiments also help resolving ambiguities for VC, where CO2 activation was unexpected due to low adsorption energy, but could be related to kinetic trapping involving a desorption barrier. With a wealth of data reported and direct experimental evidence provided, this study aims to motivate further basic surface science experiments on an interesting case of CO2 activating materials, allowing also for a benchmark of employed theoretical models.},
doi = {10.1021/acs.jpcc.7b12227},
journal = {Journal of Physical Chemistry. C},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {1}
}