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

Abstract

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, butmore » 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.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [1]
  1. Michigan Technological Univ., Houghton, MI (United States)
  2. Yangzhou Univ. (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1530524
Alternate Identifier(s):
OSTI ID: 1568928
Report Number(s):
BNL-211823-2019-JAAM
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 2; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; single-atom catalyst; methane reforming; methanol synthesis; molybdenum sulfide; DFT

Citation Formats

Zhang, Hao-Tian, Liu, Cheng, Liu, Ping, and Hu, Yun Hang. Mo6S8-based single-metal-atom catalysts for direct methane to methanol conversion. United States: N. p., 2019. Web. doi:10.1063/1.5110875.
Zhang, Hao-Tian, Liu, Cheng, Liu, Ping, & Hu, Yun Hang. Mo6S8-based single-metal-atom catalysts for direct methane to methanol conversion. United States. doi:10.1063/1.5110875.
Zhang, Hao-Tian, Liu, Cheng, Liu, Ping, and Hu, Yun Hang. Wed . "Mo6S8-based single-metal-atom catalysts for direct methane to methanol conversion". United States. doi:10.1063/1.5110875. https://www.osti.gov/servlets/purl/1530524.
@article{osti_1530524,
title = {Mo6S8-based single-metal-atom catalysts for direct methane to methanol conversion},
author = {Zhang, Hao-Tian and Liu, Cheng and Liu, Ping and Hu, Yun Hang},
abstractNote = {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.},
doi = {10.1063/1.5110875},
journal = {Journal of Chemical Physics},
number = 2,
volume = 151,
place = {United States},
year = {2019},
month = {7}
}

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Works referenced in this record:

Stable Pd-Doped Ceria Structures for CH 4 Activation and CO Oxidation
journal, November 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

  • Yumura, Takashi; Amenomori, Tatsuhiko; Kagawa, Yoshihisa
  • The Journal of Physical Chemistry A, Vol. 106, Issue 4
  • DOI: 10.1021/jp0122225

Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature
journal, April 2016


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

  • Zuo, Zhijun; Ramírez, Pedro J.; Senanayake, Sanjaya D.
  • Journal of the American Chemical Society, Vol. 138, Issue 42
  • DOI: 10.1021/jacs.6b08668

Catalysis by Supported Single Metal Atoms
journal, November 2016


Stepwise Methane-to-Methanol Conversion on CuO/SBA-15
journal, July 2018

  • Le, Ha V.; Parishan, Samira; Sagaltchik, Anton
  • Chemistry - A European Journal, Vol. 24, Issue 48
  • DOI: 10.1002/chem.201801135

Methane Emissions from the Natural Gas Transmission and Storage System in the United States
journal, July 2015

  • Zimmerle, Daniel J.; Williams, Laurie L.; Vaughn, Timothy L.
  • Environmental Science & Technology, Vol. 49, Issue 15
  • DOI: 10.1021/acs.est.5b01669

The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment
journal, November 2017

  • Ravi, Manoj; Ranocchiari, Marco; van Bokhoven, Jeroen A.
  • Angewandte Chemie International Edition, Vol. 56, Issue 52
  • DOI: 10.1002/anie.201702550

A bridge to nowhere: methane emissions and the greenhouse gas footprint of natural gas
journal, May 2014

  • Howarth, Robert W.
  • Energy Science & Engineering, Vol. 2, Issue 2
  • DOI: 10.1002/ese3.35

Density functional theory study on water–gas-shift reaction over molybdenum disulfide
journal, August 2009


Structure, Activity, and Stability of Atomically Dispersed Rh in Methane Steam Reforming
journal, March 2014

  • Duarte, R. B.; Krumeich, F.; van Bokhoven, J. A.
  • ACS Catalysis, Vol. 4, Issue 5
  • DOI: 10.1021/cs400979q

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


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

  • Ye, Shengfa; Geng, Cai-Yun; Shaik, Sason
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 21
  • DOI: 10.1039/c3cp00080j

Methanol Synthesis from H 2 and CO 2 on a Mo 6 S 8 Cluster: A Density Functional Study
journal, March 2010

  • Liu, Ping; Choi, YongMan; Yang, Yixiong
  • The Journal of Physical Chemistry A, Vol. 114, Issue 11
  • DOI: 10.1021/jp906780a

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol
journal, June 2015

  • Grundner, Sebastian; Markovits, Monica A. C.; Li, Guanna
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8546

Isothermal Cyclic Conversion of Methane into Methanol over Copper-Exchanged Zeolite at Low Temperature
journal, March 2016

  • Tomkins, Patrick; Mansouri, Ali; Bozbag, Selmi E.
  • Angewandte Chemie International Edition, Vol. 55, Issue 18
  • DOI: 10.1002/anie.201511065

Role of alkali promoters in K/MoS2 catalysts for CO-H2 reactions
journal, March 1994


Ethanol synthesis catalyzed by single Ni atom supported on Mo 6 S 8 support
journal, March 2018


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

Two-step concerted mechanism for methane hydroxylation on the diiron active site of soluble methane monooxygenase
journal, January 2000


Computationally Exploring Confinement Effects in the Methane-to-Methanol Conversion Over Iron-Oxo Centers in Zeolites
journal, November 2016

  • Göltl, Florian; Michel, Carine; Andrikopoulos, Prokopis C.
  • ACS Catalysis, Vol. 6, Issue 12
  • DOI: 10.1021/acscatal.6b02640

Insight into the Mechanism of Reverse Water-gas Shift Reaction and Ethanol Formation Catalyzed by Mo 6 S 8 -TM Clusters
journal, October 2017


Theoretical surface science and catalysis—calculations and concepts
book, January 2000


Steam-methane reforming at low temperature on nickel-based catalysts
journal, January 2014

  • Nieva, María A.; Villaverde, María M.; Monzón, Antonio
  • Chemical Engineering Journal, Vol. 235
  • DOI: 10.1016/j.cej.2013.09.030

Stability and reactivity of copper oxo-clusters in ZSM-5 zeolite for selective methane oxidation to methanol
journal, June 2016


Direct Conversion of Methane to Methanol under Mild Conditions over Cu-Zeolites and beyond
journal, January 2017

  • Tomkins, Patrick; Ranocchiari, Marco; van Bokhoven, Jeroen A.
  • Accounts of Chemical Research, Vol. 50, Issue 2
  • DOI: 10.1021/acs.accounts.6b00534

Dry Reforming of Methane on Single-Site Ni/MgO Catalysts: Importance of Site Confinement
journal, September 2018


Direct Methane−Methanol and Benzene−Phenol Conversions on Fe−ZSM-5 Zeolite:  Theoretical Predictions on the Reaction Pathways and Energetics
journal, February 2000

  • Yoshizawa, Kazunari; Shiota, Yoshihito; Yumura, Takashi
  • The Journal of Physical Chemistry B, Vol. 104, Issue 4
  • DOI: 10.1021/jp991844b

Strategies for the Direct Catalytic Valorization of Methane Using Heterogeneous Catalysis: Challenges and Opportunities
journal, April 2016

  • Olivos-Suarez, Alma I.; Szécsényi, Àgnes; Hensen, Emiel J. M.
  • ACS Catalysis, Vol. 6, Issue 5
  • DOI: 10.1021/acscatal.6b00428

Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects
journal, March 2017


Projector augmented-wave method
journal, December 1994


Methane to Methanol: Structure–Activity Relationships for Cu-CHA
journal, October 2017

  • Pappas, Dimitrios K.; Borfecchia, Elisa; Dyballa, Michael
  • Journal of the American Chemical Society, Vol. 139, Issue 42
  • DOI: 10.1021/jacs.7b06472

Selective anaerobic oxidation of methane enables direct synthesis of methanol
journal, May 2017

  • Sushkevich, Vitaly L.; Palagin, Dennis; Ranocchiari, Marco
  • Science, Vol. 356, Issue 6337
  • DOI: 10.1126/science.aam9035

Structure of the key species in the enzymatic oxidation of methane to methanol
journal, January 2015

  • Banerjee, Rahul; Proshlyakov, Yegor; Lipscomb, John D.
  • Nature, Vol. 518, Issue 7539
  • DOI: 10.1038/nature14160

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

Nanoceria-Supported Single-Atom Platinum Catalysts for Direct Methane Conversion
journal, April 2018


Theoretical study on the reaction mechanism of reverse water–gas shift reaction using a Rh–Mo 6 S 8 cluster
journal, January 2016

  • Cao, Zhaoru; Guo, Ling; Liu, Naying
  • RSC Advances, Vol. 6, Issue 110
  • DOI: 10.1039/c6ra23855f

Direct partial oxidation of methane to methanol: Reaction zones and role of catalyst location
journal, March 2008


Optimization methods for finding minimum energy paths
journal, April 2008

  • Sheppard, Daniel; Terrell, Rye; Henkelman, Graeme
  • The Journal of Chemical Physics, Vol. 128, Issue 13
  • DOI: 10.1063/1.2841941

Paths to which the nudged elastic band converges
journal, February 2011

  • Sheppard, Daniel; Henkelman, Graeme
  • Journal of Computational Chemistry, Vol. 32, Issue 8
  • DOI: 10.1002/jcc.21748

Controlled Oxidation of Hydrocarbons by the Membrane-Bound Methane Monooxygenase: The Case for a Tricopper Cluster
journal, August 2008

  • Chan, Sunney I.; Yu, Steve S. -F.
  • Accounts of Chemical Research, Vol. 41, Issue 8
  • DOI: 10.1021/ar700277n

Direct Methane to Methanol: The Selectivity–Conversion Limit and Design Strategies
journal, June 2018

  • Latimer, Allegra A.; Kakekhani, Arvin; Kulkarni, Ambarish R.
  • ACS Catalysis, Vol. 8, Issue 8
  • DOI: 10.1021/acscatal.8b00220

Hydrogen production by methane decomposition: A review
journal, February 2010


Density Functional Theory Study of CO Hydrogenation on a MoS 2 Surface
journal, March 2009

  • Huang, Min; Cho, Kyeongjae
  • The Journal of Physical Chemistry C, Vol. 113, Issue 13
  • DOI: 10.1021/jp807705y

Support Effects in Single-Atom Platinum Catalysts for Electrochemical Oxygen Reduction
journal, January 2017


Direct Conversion of Methane to Methanol by Metal-Exchanged ZSM-5 Zeolite (Metal = Fe, Co, Ni, Cu)
journal, November 2016

  • Mahyuddin, M. Haris; Staykov, Aleksandar; Shiota, Yoshihito
  • ACS Catalysis, Vol. 6, Issue 12
  • DOI: 10.1021/acscatal.6b01721

Catalytic performance of mesoporous VOx/SBA-15 catalysts for the partial oxidation of methane to formaldehyde
journal, August 2003


Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22
  • DOI: 10.1063/1.1323224

Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen
journal, May 2014


A high performance catalyst for methane conversion to methanol: graphene supported single atom Co
journal, January 2018

  • Yuan, Jinyun; Zhang, Wenhua; Li, Xingxing
  • Chemical Communications, Vol. 54, Issue 18
  • DOI: 10.1039/c7cc08713f

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Efficient Oxidation of Methane to Methanol by Dioxygen Mediated by Tricopper Clusters
journal, February 2013

  • Chan, Sunney I.; Lu, Yu-Jhang; Nagababu, Penumaka
  • Angewandte Chemie International Edition, Vol. 52, Issue 13
  • DOI: 10.1002/anie.201209846

Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation
journal, January 2018

  • Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei
  • Nature Chemistry, Vol. 10, Issue 3
  • DOI: 10.1038/nchem.2915

Mechanistic Study of Methanol Synthesis from CO 2 and H 2 on a Modified Model Mo 6 S 8 Cluster
journal, January 2015


Understanding trends in C–H bond activation in heterogeneous catalysis
journal, October 2016

  • Latimer, Allegra A.; Kulkarni, Ambarish R.; Aljama, Hassan
  • Nature Materials, Vol. 16, Issue 2
  • DOI: 10.1038/nmat4760

A generalized solid-state nudged elastic band method
journal, February 2012

  • Sheppard, Daniel; Xiao, Penghao; Chemelewski, William
  • The Journal of Chemical Physics, Vol. 136, Issue 7
  • DOI: 10.1063/1.3684549

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts
journal, November 2017

  • Shan, Junjun; Li, Mengwei; Allard, Lawrence F.
  • Nature, Vol. 551, Issue 7682
  • DOI: 10.1038/nature24640

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