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

Title: Promotion of catalytic selectivity on transition metal oxide through restructuring surface lattice

Journal Article · · Applied Catalysis. B, Environmental
 [1];  [2];  [3];  [3];  [4];  [4];  [4];  [3];  [2];  [4]
  1. University of Kansas, Lawrence, KS (United States); Zhejiang University, Hangzhou (China); Hangzhou Dianzi University (China)
  2. University of California, Riverside, CA (United States)
  3. Zhejiang University, Hangzhou (China)
  4. University of Kansas, Lawrence, KS (United States)
+ Show Author Affiliations

Pursuit of high catalytic selectivity is paramount in the design of catalysts for green chemical processes towards minimizing the production of undesired products. We demonstrated that catalytic selectivity for production of alkene through oxidative dehydrogenation of alkane on transition metal oxides can be promoted through tailoring the surface lattice of the oxide catalyst. Selectivity for production of ethylene through oxidative dehydrogenation (ODH) of ethane on Co3O4 nanocrystals can be substantially increased by 30%–35% via temperature-mediated reconstruction of surface lattice of Co3O4. Co3O4 nanocrystals formed at 800 °C leads to smooth, flat crystal plane with predominantly exposed (111) facet in contrast to high Miller index (311) facet of Co3O4 formed at ≤700 °C, revealed by environmental transmission electron microscopy. Isotope-labelled experiments suggest that the higher catalytic selectivity on the (111) facet results from the lower activity of its surface lattice oxygen atoms. Consistent with these experimental results, DFT calculations suggest low activity of surface lattice oxygen atoms and high activation barriers for adsorption and dissociation of C—H bond on the (111) surface in contrast to (311). Upon the activation of C—H on (311), the stronger binding of ethylene on more active, under-coordinated surface lattice oxygen atoms of (311) forms a robust “deprotonated ethylene glycol”-like intermediate on (311) with a rate-limiting desorption barrier to the formation of ethylene. Compared to (311), the kinetically favorable desorption of bound ethylene species from (111) surface well rationalized the higher selectivity for production of ethylene on (111) than (311). Here these findings demonstrate that temperature-mediated tailoring of the surface lattice for a transition metal oxide nanocatalyst is a promising approach in pursuing high selectivity in oxidative dehydrogenation of hydrocarbons.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); University of Kansas, Lawrence, KS (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Natural Science Foundation of China
Grant/Contract Number:
SC0014561
OSTI ID:
1543507
Journal Information:
Applied Catalysis. B, Environmental, Journal Name: Applied Catalysis. B, Environmental Journal Issue: C Vol. 237; ISSN 0926-3373
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (55)

Co3O4 Nanomaterials in Lithium-Ion Batteries and Gas Sensors journal May 2005
Transition Metal Oxide Work Functions: The Influence of Cation Oxidation State and Oxygen Vacancies journal June 2012
Porous Co3O4 Nanotubes Derived From Co4(CO)12 Clusters on Carbon Nanotube Templates: A Highly Efficient Material For Li-Battery Applications journal December 2007
Oxygen Storage at the Metal/Oxide Interface of Catalyst Nanoparticles journal November 2005
On the Role of Oxygen Defects in the Catalytic Performance of Zinc Oxide journal April 2006
Catalytic Oxidation of Carbon Monoxide over Transition Metal Oxides journal December 2010
Oxygen Vacancy: The Invisible Agent on Oxide Surfaces journal October 2003
The role of oxygen vacancies on ceria surfaces in the oxidation of carbon monoxide journal September 1994
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Total oxidation of propene at low temperature over Co3O4–CeO2 mixed oxides: Role of surface oxygen vacancies and bulk oxygen mobility in the catalytic activity journal September 2008
Oxygen vacancies in transition metal and rare earth oxides: Current state of understanding and remaining challenges journal June 2007
The electronic structure of oxygen vacancy defects at the low index surfaces of ceria journal December 2005
In-Situ Studies of Nanocatalysis journal April 2013
Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results journal May 1995
Recent Advances in Transition Metal Catalyzed Oxidation of Organic Substrates with Molecular Oxygen journal June 2005
Atomic-Scale Observations of Catalyst Structures under Reaction Conditions and during Catalysis journal March 2016
Heterogeneous Catalysis journal February 1998
General Rules for Predicting Where a Catalytic Reaction Should Occur on Metal Surfaces:  A Density Functional Theory Study of C−H and C−O Bond Breaking/Making on Flat, Stepped, and Kinked Metal Surfaces journal February 2003
Catalytic CO Oxidation by a Gold Nanoparticle:  A Density Functional Study journal September 2002
CO Oxidation on Au n /TiO 2 Catalysts Produced by Size-Selected Cluster Deposition journal May 2004
Selective Synthesis of Co 3 O 4 Nanocrystal with Different Shape and Crystal Plane Effect on Catalytic Property for Methane Combustion journal December 2008
Surface Restructuring of Nanoparticles:  An Efficient Route for Ligand−Metal Oxide Crosstalk journal October 2002
Low-Temperature Synthesis of Tunable Mesoporous Crystalline Transition Metal Oxides and Applications as Au Catalyst Supports journal August 2008
Toward the Nanoscopic “Electronic Nose”:  Hydrogen vs Carbon Monoxide Discrimination with an Array of Individual Metal Oxide Nano- and Mesowire Sensors journal July 2006
Restructuring Transition Metal Oxide Nanorods for 100% Selectivity in Reduction of Nitric Oxide with Carbon Monoxide journal June 2013
Single-atom catalysis of CO oxidation using Pt1/FeOx journal July 2011
The role of steps in surface catalysis and reaction oscillations journal July 2010
Atomic origins of the high catalytic activity of nanoporous gold journal August 2012
The role of low-coordinate oxygen on Co 3 O 4 (110) in catalyticCO oxidation journal January 2011
Size- and shape-dependent catalytic performances of oxidation and reduction reactions on nanocatalysts journal January 2016
Understanding oxidative dehydrogenation of ethane on Co 3 O 4 nanorods from density functional theory journal January 2016
Oxide ultra-thin films on metals: new materials for the design of supported metal catalysts journal January 2008
The nature of the active site in heterogeneous metal catalysis journal January 2008
Action of bimetallic nanocatalysts under reaction conditions and during catalysis: evolution of chemistry from high vacuum conditions to reaction conditions journal January 2012
High surface area mesoporous Co3O4 from a direct soft template route journal January 2012
Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications journal January 2013
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal October 1999
Heterogeneous-Homogeneous Mechanism of Catalytic Oxidation journal December 1989
A novel process from cobalt nanowire to Co3O4nanotube journal September 2004
Special points for Brillouin-zone integrations journal June 1976
Projector augmented-wave method journal December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Composition, structure, and stability of RuO 2 ( 110 ) as a function of oxygen pressure journal December 2001
Generalized Gradient Approximation Made Simple journal October 1996
Oxygen-Mediated Diffusion of Oxygen Vacancies on the TiO2(110) Surface journal December 2002
The Impact of Nanoscience on Heterogeneous Catalysis journal March 2003
Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts journal August 2003
Charging Effects on Bonding and Catalyzed Oxidation of CO on Au8 Clusters on MgO journal January 2005
Electron Localization Determines Defect Formation on Ceria Substrates journal July 2005
Break-Up of Stepped Platinum Catalyst Surfaces by High CO Coverage journal February 2010
Ceria Maintains Smaller Metal Catalyst Particles by Strong Metal-Support Bonding journal August 2010
In Situ Studies of Chemistry and Structure of Materials in Reactive Environments journal January 2011
The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts journal April 2012

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
42 ENGINEERING
cobalt oxide
oxygen vacancies
selectivity
surface faceting