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Title: Combining Theory and Experiment for Multitechnique Characterization of Activated CO2 on Transition Metal Carbide (001) Surfaces

Abstract

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 evidencemore » 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.« 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:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1425041
Report Number(s):
BNL-200037-2018-JAAM
Journal ID: ISSN 1932-7447; TRN: US1802010
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 13; 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

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., 2018. 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. Mon . "Combining Theory and Experiment for Multitechnique Characterization of Activated CO2 on Transition Metal Carbide (001) Surfaces". United States. doi:10.1021/acs.jpcc.7b12227. https://www.osti.gov/servlets/purl/1425041.
@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 = 13,
volume = 123,
place = {United States},
year = {2018},
month = {1}
}

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Figures / Tables:

Table 1 Table 1: Adsorption energies (Eads in eV), net charge transfer ΔQ (in e) and induced work function change Δϕ (in eV) for CO2 adsorption on the different TMC (001) surfaces. Adsorption energies at the PBE (-D3) level of theory have been reproduced from Ref. 18 and include zero point energymore » (ZPE) contributions« less

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