Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Ni-Doping Effects on Oxygen Removal from an Orthorhombic Mo2C (001) Surface: A Density Functional Theory Study

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [1];  [2];  [2]
  1. Kansas State Univ., Manhattan, KS (United States). Dept. of Chemical Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations

Density functional theory (DFT) calculations were used in this paper to investigate the effect of Ni dopants on the removal of chemisorbed oxygen (O*) from the Mo-terminated (TMo) and C-terminated (TC) Mo2C(001) surfaces. The removal of adsorbed oxygen from the catalytic site is essential to maintain the long-term activity and selectivity of the carbide catalysts in the deoxygenation process related to bio-oil stabilization and upgrading. In this contribution, the computed reaction energetics and reaction barriers of O* removal were compared among undoped and Ni-doped Mo2C(001) surfaces. The DFT calculations indicate that selected Ni-doped surfaces such as Ni adsorbed on TMo and TC Mo2C(001) surfaces enable weaker binding of important reactive intermediates (O*, OH*) compared to the undoped counterparts, which is beneficial for the O* removal from the catalyst surface. This study thus confirms the promoting effect of the Ni dopant on O* removal reaction on the TMo Mo2C(001) and TC Mo2C(001) surfaces. Finally, this computational prediction has been confirmed by the temperature-programmed reduction profiles of Mo2C and Ni-doped Mo2C catalysts, which had been passivated and stored in an oxygen environment.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation and Fuels. Bioenergy Technologies Office (BETO); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357; AC02-05CH11231
OSTI ID:
1423017
Alternate ID(s):
OSTI ID: 1425276
Journal Information:
Journal of Physical Chemistry. C, Vol. 122, Issue 3; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (39)

Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass journal September 2007
Processing biomass in conventional oil refineries: Production of high quality diesel by hydrotreating vegetable oils in heavy vacuum oil mixtures journal October 2007
Production of High-Quality Diesel from Biomass Waste Products journal January 2011
Critical design of heterogeneous catalysts for biomass valorization: current thrust and emerging prospects journal January 2016
Trends in the Surface and Catalytic Chemistry of Transition-Metal Ceramics in the Deoxygenation of a Woody Biomass Pyrolysis Model Compound journal April 2017
Surface Chemistry of Transition Metal Carbides journal January 2005
Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis journal September 2012
Selective Hydrodeoxygenation of Biomass-Derived Oxygenates to Unsaturated Hydrocarbons using Molybdenum Carbide Catalysts journal April 2013
Controlling C–O, C–C and C–H bond scission for deoxygenation, reforming, and dehydrogenation of ethanol using metal-modified molybdenum carbide surfaces journal January 2014
Vapor phase hydrodeoxygenation of furfural to 2-methylfuran on molybdenum carbide catalysts journal January 2014
Catalytic hydrodeoxygenation of palmitic acid over a bifunctional Co-doped MoO 2 /CNTs catalyst: an insight into the promoting effect of cobalt journal January 2016
Ni-modified Mo2C catalysts for methane dry reforming journal July 2012
Ni-Doping Effects on Carbon Diffusion and Oxidation over Mo 2 C Surfaces journal September 2013
Iron-Doped Molybdenum Carbide Catalyst with High Activity and Stability for the Hydrogen Evolution Reaction journal June 2015
Molybdenum Carbides, Active and In Situ Regenerable Catalysts in Hydroprocessing of Fast Pyrolysis Bio-Oil journal May 2016
Catalytic Activities of NiMo Carbide Supported on SiO2 for the Hydrodeoxygenation of Ethyl Benzoate, Acetone, and Acetaldehyde journal March 2010
Catalytic Activity and Stability of Nickel-Modified Molybdenum Carbide Catalysts for Steam Reforming of Methanol journal April 2014
Understanding trends in hydrodeoxygenation reactivity of metal and bimetallic alloy catalysts from ethanol reaction on stepped surface journal September 2017
Trends in the Hydrodeoxygenation Activity and Selectivity of Transition Metal Surfaces journal September 2014
Density Functional Study of the Adsorption of Atomic Oxygen on the (001) Surface of Early Transition-Metal Carbides journal December 2006
Atomic and electronic structure of molybdenum carbide phases: bulk and low Miller-index surfaces journal January 2013
Stable surface terminations of orthorhombic Mo2C catalysts and their CO activation mechanisms journal May 2014
Surface morphology of orthorhombic Mo2C catalyst and high coverage hydrogen adsorption journal September 2016
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium journal May 1994
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Generalized Gradient Approximation Made Simple journal October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Special points for Brillouin-zone integrations journal June 1976
High-precision sampling for Brillouin-zone integration in metals journal August 1989
Neutron powder diffraction studies of transition metal hemicarbides M2C1−x—II. In situ high temperature study on W2C1−x and Mo2C1−x journal August 1988
A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal December 2000
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal October 1999
Ni-doped Mo 2 C nanowires supported on Ni foam as a binder-free electrode for enhancing the hydrogen evolution performance journal January 2015
A fast and robust algorithm for Bader decomposition of charge density journal June 2006
A grid-based Bader analysis algorithm without lattice bias journal January 2009
Catalytic deoxygenation on transition metal carbide catalysts journal January 2016
Water gas shift reaction kinetics and reactor modeling for fuel cell grade hydrogen journal November 2003
Structural Evolution of Molybdenum Carbides in Hot Aqueous Environments and Impact on Low-Temperature Hydroprocessing of Acetic Acid journal March 2015
Experimental and Computational Investigation of Acetic Acid Deoxygenation over Oxophilic Molybdenum Carbide: Surface Chemistry and Active Site Identity journal January 2016

Cited By (2)

Non‐3d Metal Modulation of a 2D Ni–Co Heterostructure Array as Multifunctional Electrocatalyst for Portable Overall Water Splitting journal March 2020
Surface and Interface Engineering: Molybdenum Carbide–Based Nanomaterials for Electrochemical Energy Conversion journal September 2019

Figures / Tables (7)

Figure 1(p. 6)figure Figure 1
Figure 2(p. 9)figure Figure 2
Table 1(p. 9)table Table 1
Figure 3(p. 11)figure Figure 3
Table 2(p. 12)table Table 2
Figure 4(p. 15)figure Figure 4
Figure 5(p. 16)figure Figure 5

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY