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

Abstract

Density functional theory (DFT) calculations were used to investigate the effect of Ni dopants on the removal of chemisorbed oxygen (O*) from the Mo-terminated (T-Mo) 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 T-Mo 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 T-Mo Mo2C(001) and Tc Mo2C(001) surfaces. 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.

Authors:
 [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)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1423017
Alternate Identifier(s):
OSTI ID: 1425276
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 3; 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

Zhou, Mingxia, Cheng, Lei, Choi, Jae-Soon, Liu, Bin, Curtiss, Larry A., and Assary, Rajeev S. Ni-Doping Effects on Oxygen Removal from an Orthorhombic Mo2C (001) Surface: A Density Functional Theory Study. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpcc.7b09870.
Zhou, Mingxia, Cheng, Lei, Choi, Jae-Soon, Liu, Bin, Curtiss, Larry A., & Assary, Rajeev S. Ni-Doping Effects on Oxygen Removal from an Orthorhombic Mo2C (001) Surface: A Density Functional Theory Study. United States. https://doi.org/10.1021/acs.jpcc.7b09870
Zhou, Mingxia, Cheng, Lei, Choi, Jae-Soon, Liu, Bin, Curtiss, Larry A., and Assary, Rajeev S. Fri . "Ni-Doping Effects on Oxygen Removal from an Orthorhombic Mo2C (001) Surface: A Density Functional Theory Study". United States. https://doi.org/10.1021/acs.jpcc.7b09870. https://www.osti.gov/servlets/purl/1423017.
@article{osti_1423017,
title = {Ni-Doping Effects on Oxygen Removal from an Orthorhombic Mo2C (001) Surface: A Density Functional Theory Study},
author = {Zhou, Mingxia and Cheng, Lei and Choi, Jae-Soon and Liu, Bin and Curtiss, Larry A. and Assary, Rajeev S.},
abstractNote = {Density functional theory (DFT) calculations were used to investigate the effect of Ni dopants on the removal of chemisorbed oxygen (O*) from the Mo-terminated (T-Mo) 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 T-Mo 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 T-Mo Mo2C(001) and Tc Mo2C(001) surfaces. 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.},
doi = {10.1021/acs.jpcc.7b09870},
journal = {Journal of Physical Chemistry. C},
number = 3,
volume = 122,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

Figure 1 Figure 1: Top view and side view of optimized structures of Mo2C(001) surfaces. (a) un-doped TMo Mo2C(001) surface, (b) un-doped TC Mo2C(001) surface. The top two layers of Mo atoms are depicted in different color to differentiate Mo on different positions. Same color scheme is utilized throughout the paper.

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Works referenced in this record:

Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass
journal, September 2007

  • Huber, George W.; Corma, Avelino
  • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7184-7201
  • DOI: 10.1002/anie.200604504

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

  • Corma, Avelino; de la Torre, Olalla; Renz, Michael
  • Angewandte Chemie International Edition, Vol. 50, Issue 10
  • DOI: 10.1002/anie.201007508

Critical design of heterogeneous catalysts for biomass valorization: current thrust and emerging prospects
journal, January 2016

  • De, Sudipta; Dutta, Saikat; Saha, Basudeb
  • Catalysis Science & Technology, Vol. 6, Issue 20
  • DOI: 10.1039/C6CY01370H

Surface Chemistry of Transition Metal Carbides
journal, January 2005

  • Hwu, Henry H.; Chen, Jingguang G.
  • Chemical Reviews, Vol. 105, Issue 1
  • DOI: 10.1021/cr0204606

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


Vapor phase hydrodeoxygenation of furfural to 2-methylfuran on molybdenum carbide catalysts
journal, January 2014

  • Lee, Wen-Sheng; Wang, Zhenshu; Zheng, Weiqing
  • Catalysis Science & Technology, Vol. 4, Issue 8
  • DOI: 10.1039/c4cy00286e

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

  • Ding, Ranran; Wu, Yulong; Chen, Yu
  • Catalysis Science & Technology, Vol. 6, Issue 7
  • DOI: 10.1039/C5CY01575H

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

  • Zhao, Yonghui; Li, Shenggang; Sun, Yuhan
  • The Journal of Physical Chemistry C, Vol. 117, Issue 37
  • DOI: 10.1021/jp405209c

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

  • Zhang, Wei; Zhang, Ye; Zhao, Liangfu
  • Energy & Fuels, Vol. 24, Issue 3, p. 2052-2059
  • DOI: 10.1021/ef901222z

Catalytic Activity and Stability of Nickel-Modified Molybdenum Carbide Catalysts for Steam Reforming of Methanol
journal, April 2014

  • Ma, Yufei; Guan, Guoqing; Phanthong, Patchiya
  • The Journal of Physical Chemistry C, Vol. 118, Issue 18
  • DOI: 10.1021/jp501021t

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

  • Viñes, F.; Sousa, C.; Illas, F.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 3
  • DOI: 10.1021/jp065126i

Atomic and electronic structure of molybdenum carbide phases: bulk and low Miller-index surfaces
journal, January 2013

  • Politi, José Roberto dos Santos; Viñes, Francesc; Rodriguez, Jose A.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 30
  • DOI: 10.1039/c3cp51389k

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

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

High-precision sampling for Brillouin-zone integration in metals
journal, August 1989


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 111, Issue 15
  • DOI: 10.1063/1.480097

Ni-doped Mo 2 C nanowires supported on Ni foam as a binder-free electrode for enhancing the hydrogen evolution performance
journal, January 2015

  • Xiong, Kun; Li, Li; Zhang, Li
  • Journal of Materials Chemistry A, Vol. 3, Issue 5
  • DOI: 10.1039/C4TA05686H

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

  • Sullivan, Mark M.; Chen, Cha-Jung; Bhan, Aditya
  • Catalysis Science & Technology, Vol. 6, Issue 3
  • DOI: 10.1039/C5CY01665G

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

  • Choi, Jae-Soon; Schwartz, Viviane; Santillan-Jimenez, Eduardo
  • Catalysts, Vol. 5, Issue 1
  • DOI: 10.3390/catal5010406

Experimental and Computational Investigation of Acetic Acid Deoxygenation over Oxophilic Molybdenum Carbide: Surface Chemistry and Active Site Identity
journal, January 2016

  • Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.
  • ACS Catalysis, Vol. 6, Issue 2
  • DOI: 10.1021/acscatal.5b01930

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