Title: Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking

Journal Article · · Journal of the American Chemical Society
 [1];  [2];  [3];  [4];  [5];  [2];  [3];  [5];  [6];  [2]; ORCiD logo [2]
  1. Instituto de Fisica Rosario (IFIR), Santa Fe (Argentina)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Univ. Central de Venezuela, Caracas (Venezuela)
  4. Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.
  5. Charles Univ., Prague (Czech Republic)
  6. Instituto de Catalisis y Petroleoquimica, Madrid (Spain)
+ Show Author Affiliations

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH4 → CH3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy and density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012704
OSTI ID:
1440348
Report Number(s):
BNL-205725-2018-JAAM
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 24 Vol. 140; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (11)

Tuning the Structure of Pt Nanoparticles through Support Interactions: An in Situ Polarized X-ray Absorption Study Coupled with Atomistic Simulations journal March 2019
Palladium Dimer Supported on Mo 2 CO 2 (MXene) for Direct Methane to Methanol Conversion journal September 2018
A Supported Nickel Catalyst Stabilized by a Surface Digging Effect for Efficient Methane Oxidation journal November 2019
A Supported Nickel Catalyst Stabilized by a Surface Digging Effect for Efficient Methane Oxidation journal November 2019
Thermodynamic Limitations of the Catalyst Design Space for Methanol Production from Methane journal October 2018
Methane Activation by (n=0, 1, 2; m= 1, 2): Reactivity Parameters, Electronic Properties and Binding Energy Analysis journal July 2019
Controlling the Reduction Extent for Metal Catalysts journal May 2019
Structure and bonding in NbX5 X = (F, Cl, Br and I) complexes: a molecular orbital perspective in the C–H bond activation journal October 2018
Selective oxidation of methane to methanol with H 2 O 2 over an Fe-MFI zeolite catalyst using sulfolane solvent journal January 2019
Zeolite acidity strongly influences hydrogen peroxide activation and oxygenate selectivity in the partial oxidation of methane over M,Fe-MFI (M: Ga, Al, B) zeolites journal January 2019
Quasicatalytic and catalytic selective oxidation of methane to methanol over solid materials: a review on the roles of water journal October 2019

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