skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Journal Article · · Journal of Physical Chemistry. C
 [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)
+ Show Author Affiliations

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.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1425041
Report Number(s):
BNL-200037-2018-JAAM; TRN: US1802010
Journal Information:
Journal of Physical Chemistry. C, Vol. 123, Issue 13; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

References (57)

Surface chemistry of carbon dioxide journal January 1996
Surface science perspective of carbon dioxide chemistry—Adsorption kinetics and dynamics of CO2 on selected model surfaces journal November 2009
Surface chemistry of carbon dioxide revisited journal December 2016
Measurement, Standards, and Data Needs for CO 2 Capture Materials: A Critical Review journal October 2013
Carbon Dioxide Capture: Prospects for New Materials journal July 2010
Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis journal August 1973
Surface Chemistry of Transition Metal Carbides journal January 2005
Fundamentals of Methanol Synthesis on Metal Carbide Based Catalysts: Activation of CO2 and H2 journal December 2014
The bending machine: CO 2 activation and hydrogenation on δ-MoC(001) and β-Mo 2 C(001) surfaces journal January 2014
Activation mechanisms of H 2 , O 2 , H 2 O, CO 2 , CO, CH 4 and C 2 H x on metallic Mo 2 C(001) as well as Mo/C terminated Mo 2 C(101) from density functional theory computations journal August 2016
Density functional theory study into the adsorption of CO2, H and CHx (x=0–3) as well as C2H4 on α-Mo2C(0001) journal June 2006
Effective and Highly Selective CO Generation from CO 2 Using a Polycrystalline α-Mo 2 C Catalyst journal May 2017
Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO 2 to CO journal May 2014
Identifying trends and descriptors for selective CO 2 conversion to CO over transition metal carbides journal January 2015
CO 2 Activation and Methanol Synthesis on Novel Au/TiC and Cu/TiC Catalysts journal August 2012
Adsorption, Dissociation, and Hydrogenation of CO 2 on WC(0001) and WC-Co Alloy Surfaces Investigated with Theoretical Calculations journal June 2012
Transition metal carbides as novel materials for CO 2 capture, storage, and activation journal January 2016
Surface chemistry of CO2 – Adsorption of carbon dioxide on clean surfaces at ultrahigh vacuum journal May 2014
From Local Adsorption Stresses to Chiral Surfaces:  ( R , R )-Tartaric Acid on Ni(110) journal December 2001
A multi-technique study of CO 2 adsorption on Fe 3 O 4 magnetite journal January 2017
A Multitechnique Study of CO Adsorption on the TiO 2 Anatase (101) Surface journal August 2015
Sequential carbon oxygen bond cleavage in chemisorption of CO 2 on Fe(100) journal July 1993
Interaction of carbon dioxide with Ni(110): A combined experimental and theoretical study journal November 2007
CO2 Activation by ZnO through the Formation of an Unusual Tridentate Surface Carbonate journal July 2007
Structure and Dynamics of CO 2 on Rutile TiO 2 (110)-1×1 journal October 2012
CO 2 Capture by TiO 2 Anatase Surfaces: A Combined DFT and FTIR Study journal October 2014
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Generalized Gradient Approximation Made Simple journal October 1996
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Projector augmented-wave method journal December 1994
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Special points for Brillouin-zone integrations journal June 1976
Interaction of oxygen with ZrC(001) and VC(001): Photoemission and first-principles studies journal August 2005
The interaction of oxygen with TiC(001): Photoemission and first-principles studies journal January 2004
A systematic density functional theory study of the electronic structure of bulk and (001) surface of transition-metals carbides journal May 2005
Photoemission of molecular adsorbates journal September 1988
CO2 adsorption and reaction on Fe(111): An angle resolved photoemission (ARUPS) study journal February 1987
Interaction of carbon dioxide with Fe(110), stepped Fe(100) and Fe(111) journal September 1986
Adsorption and reaction of CO2 and CO2/O CO-adsorption on Ni(110): Angle resolved photoemission (ARUPS) and electron energy loss (HREELS) studies journal January 1987
The interaction of CO2 with sodium-promoted W(011) journal January 2005
Photoemission and quantum chemical study of SrTiO 3 ( 001 ) surfaces and their interaction with CO 2 journal November 2008
Interaction of O2, CO and CO2 with Co films journal January 2005
Evidence for spontaneous CO2 activation on cobalt surfaces journal March 2008
Chemisorption of atomic chlorine on metal surfaces and the interpretation of the induced work function changes journal January 2005
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation journal September 1992
Surface-shifted N 1 s and C 1 s levels on the (100) surface of TiN and TiC journal November 1993
High-resolution core-level study of ZrC(100) and its reaction with oxygen journal July 1993
High-resolution core-level studies of VC 0.80 surfaces journal April 1993
Molecular Adsorption Changes the Quantum Structure of Oxide-Supported Gold Nanoparticles: Chemisorption versus Physisorption journal July 2015
Imaging and characterization of activated CO 2 species on Ni(110) journal October 2010
Scanning tunneling microscopy studies of niobium carbide (100) and (110) surfaces journal October 1996
Characterization of carbides by scanning tunneling microscopy journal November 1988
Ab initio reflectance difference spectra of the bare and adsorbate covered Cu(110) surfaces journal July 2007
Water adsorbate influence on the Cu(110) surface optical response journal November 2015
Linear optical properties in the projector-augmented wave methodology journal January 2006
Comparison of theoretical and experimental dielectric functions: Electron energy-loss spectroscopy and density-functional calculations on skutterudites journal December 2006
Optical study of the stoichiometry-dependent electronic structure of TiC x , VC x , and NbC x journal September 1990

Cited By (2)

Porous MoxCy/SiO2 Material for CO2 Hydrogenation journal August 2019
Core electron binding energies of adsorbates on Cu(111) from first-principles calculations journal January 2018

Figures / Tables (23)

Table 1(p. 17)table Table 1
Table 2(p. 18)table Table 2
Table 3(p. 19)table Table 3
Table 4(p. 20)table Table 4
Figure 1(p. 21)figure Figure 1
Figure 2(p. 22)figure Figure 2
Figure 3(p. 23)figure Figure 3
Figure 4(p. 24)figure Figure 4
Figure 5(p. 25)figure Figure 5
Figure 6(p. 26)figure Figure 6
Figure 7(p. 27)figure Figure 7
Figure 8(p. 28)figure Figure 8
Figure 9(p. 29)figure Figure 9
Table S1(p. 38)table Table S1
Fig. S1(p. 39)figure Fig. S1
Fig. S2(p. 40)figure Fig. S2
Fig. S3(p. 41)figure Fig. S3
Fig. S4(p. 42)figure Fig. S4
Fig. S5(p. 43)figure Fig. S5
Fig. S6(p. 44)figure Fig. S6
Fig. S7(p. 45)figure Fig. S7
Fig. S8(p. 46)figure Fig. S8
Fig. S9(p. 47)figure Fig. S9

Similar Records

Acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces: A comprehensive periodic DFT study
Journal Article · Tue Dec 06 00:00:00 EST 2016 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1425041
+2 more
Promoting effect of tungsten carbide on the catalytic activity of Cu for CO2 reduction
Journal Article · Wed Jan 01 00:00:00 EST 2020 · Physical Chemistry Chemical Physics. PCCP (Print) · OSTI ID:1425041
+1 more
Density functional theory study of mercury adsorption on metal surfaces
Journal Article · Sat Mar 01 00:00:00 EST 2008 · Physical Review B · OSTI ID:1425041

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY