Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Mo6S8-based single-metal-atom catalysts for direct methane to methanol conversion

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5110875· OSTI ID:1530524
 [1];  [2];  [3];  [1]
  1. Michigan Technological Univ., Houghton, MI (United States)
  2. Yangzhou Univ. (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations
The single atom catalysts have been attracting much attention for catalysis. Here, the significant influence of single-metal-atom (M = K, Ti, Fe, Co, Ni, Cu, Rh) doping on a Mo6S8 cluster was revealed for the direct methane to methanol conversion in water stream using density functional theory calculations. It was found that all single atom dopants help to facilitate the conversion via the steam reforming of methane (SRM). The single Fe atom on Mo6S8 (Fe—Mo6S8) exhibits the most significant promoting effect, which is followed by Ni, Co, Rh—Mo6S8 > K, Ti, Cu—Mo6S8 > Mo6S8 in a decreasing sequence. The enhanced activity by single atom doping on Mo6S8 is mainly associated with the interplay between the ensemble effect via the direct participation of an active M dopant and the site confinement imposed by doping of a single M atom, in tuning the methane conversion and methanol selectivity. It generates the new active center, M, which confines the SRM to occur at the M—Mo bridge sites and facilitates the selective production of methanol. An adequate single-atom promoter should not only bind *OH or *O moderately, being strongly enough to help water dissociation and weakly enough to allow the oxidation of methane, but also impose the confinement effect to facilitate the C—O bond association and production of methanol. Our results highlight the importance of the interplay among ligand, ensemble, and confinement effects in promoting the complex SRM over single atom catalysts.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0012704
OSTI ID:
1530524
Alternate ID(s):
OSTI ID: 1568928
Report Number(s):
BNL--211823-2019-JAAM
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 151; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (62)

Efficient Oxidation of Methane to Methanol by Dioxygen Mediated by Tricopper Clusters journal February 2013
Isothermal Cyclic Conversion of Methane into Methanol over Copper-Exchanged Zeolite at Low Temperature journal March 2016
Efficient Oxidation of Methane to Methanol by Dioxygen Mediated by Tricopper Clusters journal February 2013
Isothermal Cyclic Conversion of Methane into Methanol over Copper-Exchanged Zeolite at Low Temperature journal March 2016
The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment journal November 2017
Stepwise Methane-to-Methanol Conversion on CuO/SBA-15 journal July 2018
A bridge to nowhere: methane emissions and the greenhouse gas footprint of natural gas journal May 2014
Paths to which the nudged elastic band converges journal February 2011
Role of alkali promoters in K/MoS2 catalysts for CO-H2 reactions journal March 1994
Density functional theory study on water–gas-shift reaction over molybdenum disulfide journal August 2009
Ethanol synthesis catalyzed by single Ni atom supported on Mo 6 S 8 support journal March 2018
Steam-methane reforming at low temperature on nickel-based catalysts journal January 2014
Synthesis of methanol from methane: Challenges and advances on the multi-step (syngas) and one-step routes (DMTM) journal May 2016
Hydrogen production by methane decomposition: A review journal February 2010
Stability and reactivity of copper oxo-clusters in ZSM-5 zeolite for selective methane oxidation to methanol journal June 2016
Insight into the Mechanism of Reverse Water-gas Shift Reaction and Ethanol Formation Catalyzed by Mo 6 S 8 -TM Clusters journal October 2017
Two-step concerted mechanism for methane hydroxylation on the diiron active site of soluble methane monooxygenase journal January 2000
Theoretical surface science and catalysis—calculations and concepts book January 2000
Catalytic performance of mesoporous VOx/SBA-15 catalysts for the partial oxidation of methane to formaldehyde journal August 2003
Direct partial oxidation of methane to methanol: Reaction zones and role of catalyst location journal March 2008
Direct Conversion of Methane to Methanol under Mild Conditions over Cu-Zeolites and beyond journal January 2017
Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects journal March 2017
Methane Emissions from the Natural Gas Transmission and Storage System in the United States journal July 2015
Strategies for the Direct Catalytic Valorization of Methane Using Heterogeneous Catalysis: Challenges and Opportunities journal April 2016
Catalysis by Supported Single Metal Atoms journal November 2016
Direct Conversion of Methane to Methanol by Metal-Exchanged ZSM-5 Zeolite (Metal = Fe, Co, Ni, Cu) journal November 2016
Computationally Exploring Confinement Effects in the Methane-to-Methanol Conversion Over Iron-Oxo Centers in Zeolites journal November 2016
Support Effects in Single-Atom Platinum Catalysts for Electrochemical Oxygen Reduction journal January 2017
Stable Pd-Doped Ceria Structures for CH 4 Activation and CO Oxidation journal November 2017
Nanoceria-Supported Single-Atom Platinum Catalysts for Direct Methane Conversion journal April 2018
Direct Methane to Methanol: The Selectivity–Conversion Limit and Design Strategies journal June 2018
Dry Reforming of Methane on Single-Site Ni/MgO Catalysts: Importance of Site Confinement journal September 2018
Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature journal April 2016
Controlled Oxidation of Hydrocarbons by the Membrane-Bound Methane Monooxygenase: The Case for a Tricopper Cluster journal August 2008
Structure, Activity, and Stability of Atomically Dispersed Rh in Methane Steam Reforming journal March 2014
Mechanistic Study of Methanol Synthesis from CO 2 and H 2 on a Modified Model Mo 6 S 8 Cluster journal January 2015
Low-Temperature Conversion of Methane to Methanol on CeO x /Cu 2 O Catalysts: Water Controlled Activation of the C–H Bond journal October 2016
Methane to Methanol: Structure–Activity Relationships for Cu-CHA journal October 2017
Mechanism for the Formaldehyde to Formic Acid and the Formic Acid to Carbon Dioxide Conversions Mediated by an Iron-Oxo Species journal January 2002
Density Functional Theory Study of CO Hydrogenation on a MoS 2 Surface journal March 2009
Methanol Synthesis from H 2 and CO 2 on a Mo 6 S 8 Cluster: A Density Functional Study † journal March 2010
Direct Methane−Methanol and Benzene−Phenol Conversions on Fe−ZSM-5 Zeolite:  Theoretical Predictions on the Reaction Pathways and Energetics journal February 2000
Structure of the key species in the enzymatic oxidation of methane to methanol journal January 2015
Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts journal November 2017
Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation journal January 2018
Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol journal June 2015
Understanding trends in C–H bond activation in heterogeneous catalysis journal October 2016
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
Electronic structure analysis of multistate reactivity in transition metal catalyzed reactions: the case of C–H bond activation by non-heme iron(iv)–oxo cores journal January 2013
Theoretical study on the reaction mechanism of reverse water–gas shift reaction using a Rh–Mo 6 S 8 cluster journal January 2016
A high performance catalyst for methane conversion to methanol: graphene supported single atom Co journal January 2018
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points journal December 2000
A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal December 2000
Optimization methods for finding minimum energy paths journal April 2008
A generalized solid-state nudged elastic band method journal February 2012
Ab initiomolecular dynamics for liquid metals journal January 1993
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
Generalized Gradient Approximation Made Simple journal October 1996
Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen journal May 2014
Selective anaerobic oxidation of methane enables direct synthesis of methanol journal May 2017
Classical and Quantum Dynamics in Condensed Phase Simulations conference June 1998

Cited By (1)

Solar Driven CO2 Hydrogenation on Ti-Doped Silicon Nanocages journal November 2019

Figures / Tables (12)

Table 1(p. 30)table Table 1
Table 2(p. 31)table Table 2
Table 3(p. 31)table Table 3
Figure 1(p. 32)figure Figure 1
Figure 2(p. 33)figure Figure 2
Figure 3(p. 34)figure Figure 3
Figure 4(p. 35)figure Figure 4
Figure 5(p. 36)figure Figure 5
Figure 6(p. 37)figure Figure 6
Figure 7(p. 38)figure Figure 7
Figure 8(p. 39)figure Figure 8
Figure 9(p. 40)figure Figure 9

Similar Records

Mechanistic study of methanol synthesis from CO₂ and H₂ on a modified model Mo₆S₈ cluster
Journal Article · Sun Jan 11 19:00:00 EST 2015 · ACS Catalysis · OSTI ID:1183833
Direct Oxidation of Methane to Methanol Enabled by Electronic Atomic Monolayer–Metal Support Interaction
Journal Article · Sun Jun 02 20:00:00 EDT 2019 · ACS Catalysis · OSTI ID:1577539

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
methane reforming
methanol synthesis
molybdenum sulfide
single-atom catalyst