New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts

Sourav, Sagar; Wang, Yixiao; Kiani, Daniyal; Baltrusaitis, Jonas; Fushimi, Rebecca R.; Wachs, Israel E.

doi:10.1002/anie.202108201

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na ₂ WO ₄ /SiO ₂ Catalysts

Journal Article · Tue Aug 24 00:00:00 EDT 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202108201· OSTI ID:1814658

^[1]; ^[2]; ^[3]; ^[3]; ^[2]; ^[3]

Biological and Chemical Science and Engineering Energy Environment Science &, Technology Idaho National Laboratory Idaho Falls ID 83415 USA, Department of Chemical and Biomolecular Engineering Lehigh University Bethlehem PA 18015 USA
Biological and Chemical Science and Engineering Energy Environment Science &, Technology Idaho National Laboratory Idaho Falls ID 83415 USA
Department of Chemical and Biomolecular Engineering Lehigh University Bethlehem PA 18015 USA

Abstract

The complex structure of the catalytic active phase, and surface‐gas reaction networks have hindered understanding of the oxidative coupling of methane (OCM) reaction mechanism by supported Na ₂ WO ₄ /SiO ₂ catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H ₂ ‐TPR, TAP and steady‐state kinetics) experiments, that the long speculated crystalline Na ₂ WO ₄ active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na‐WO _x sites. Kinetic analysis via temporal analysis of products (TAP) and steady‐state OCM reaction studies demonstrate that ( i ) surface Na‐WO _x sites are responsible for selectively activating CH ₄ to C ₂ H _x and over‐oxidizing CH _y to CO and ( ii ) molten Na ₂ WO ₄ phase is mainly responsible for over‐oxidation of CH ₄ to CO ₂ and also assists in oxidative dehydrogenation of C ₂ H ₆ to C ₂ H ₄ . These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na ₂ WO ₄ /SiO ₂ catalysts.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; AC07-05ID14517

OSTI ID:: 1814658

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 39 Vol. 60; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (46)

Fluctuating Storage of the Active Phase in a Mn‐Na ₂ WO ₄ /SiO ₂ Catalyst for the Oxidative Coupling of Methane Werny, Maximilian J.; Wang, Yuanqing; Girgsdies, Frank Angewandte Chemie, Vol. 132, Issue 35 https://doi.org/10.1002/ange.202004778	journal	June 2020
Fluctuating Storage of the Active Phase in a Mn‐Na ₂ WO ₄ /SiO ₂ Catalyst for the Oxidative Coupling of Methane Werny, Maximilian J.; Wang, Yuanqing; Girgsdies, Frank Angewandte Chemie International Edition, Vol. 59, Issue 35 https://doi.org/10.1002/anie.202004778	journal	June 2020
Oxidative Coupling of Methane over W-Mn/SiO2 Catalyst Li, Shu-Ben Chinese Journal of Chemistry, Vol. 19, Issue 1 https://doi.org/10.1002/cjoc.20010190104	journal	January 2001
In-situ high-temperature Raman spectroscopic studies of the vibrational characteristics and microstructure evolution of sodium tungstate dihydrate crystal during heating and melting Wang, Jian; You, Jinglin; Wang, Min Journal of Raman Spectroscopy, Vol. 49, Issue 10 https://doi.org/10.1002/jrs.5429	journal	July 2018
Elementary Reactions in the Oxidative Coupling of Methane over Mn/Na2WO4/SiO2and Mn/Na2WO4/MgO Catalysts Pak, Sergei; Qiu, Ping; Lunsford, Jack H. Journal of Catalysis, Vol. 179, Issue 1 https://doi.org/10.1006/jcat.1998.2228	journal	October 1998
Synthesis of ethylene via oxidative coupling of methane I. Determination of active catalysts Keller, G. Journal of Catalysis, Vol. 73, Issue 1 https://doi.org/10.1016/0021-9517(82)90075-6	journal	January 1982
Mechanistic study of oxidative coupling of methane over Mn2O3Na2WO4SiO2 catalyst Wu, Jingang; Li, Shuben; Niu, Jianzhong Applied Catalysis A: General, Vol. 124, Issue 1 https://doi.org/10.1016/0926-860X(94)00245-2	journal	March 1995
Kinetics of oxidative coupling of methane: Bridging the gap between comprehension and description Sinev, M. Yu.; Fattakhova, Z. T.; Lomonosov, V. I. Journal of Natural Gas Chemistry, Vol. 18, Issue 3 https://doi.org/10.1016/S1003-9953(08)60128-0	journal	September 2009
Methane reforming with CO2 to syngas over CeO2-promoted Ni/Al2O3-ZrO2 catalysts prepared via a direct sol-gel process Li, Hansheng; Xu, Hang; Wang, Jinfu Journal of Natural Gas Chemistry, Vol. 20, Issue 1 https://doi.org/10.1016/S1003-9953(10)60156-9	journal	January 2011
Mn–Na2WO4/SiO2 as catalyst for the oxidative coupling of methane. What is really known? Arndt, S.; Otremba, T.; Simon, U. Applied Catalysis A: General, Vol. 425-426 https://doi.org/10.1016/j.apcata.2012.02.046	journal	May 2012
A kinetics study for the oxidative coupling of methane on a Mn/Na2WO4/SiO2 catalyst Tiemersma, T. P.; Tuinier, M. J.; Gallucci, F. Applied Catalysis A: General, Vol. 433-434 https://doi.org/10.1016/j.apcata.2012.05.002	journal	August 2012
Nanocatalysts for conversion of natural gas to liquid fuels and petrochemical feedstocks Gharibi, Mahtab; Zangeneh, Farnaz Tahriri; Yaripour, Fereydoon Applied Catalysis A: General, Vol. 443-444 https://doi.org/10.1016/j.apcata.2012.06.039	journal	November 2012
Silica material variation for the Mn x O y -Na 2 WO 4 /SiO 2 Yildiz, M.; Aksu, Y.; Simon, U. Applied Catalysis A: General, Vol. 525 https://doi.org/10.1016/j.apcata.2016.06.034	journal	September 2016
Microkinetics of methane oxidative coupling Sun, J.; Thybaut, J.; Marin, G. Catalysis Today, Vol. 137, Issue 1 https://doi.org/10.1016/j.cattod.2008.02.026	journal	August 2008
Direct methane conversion routes to chemicals and fuels Alvarez-Galvan, M. C.; Mota, N.; Ojeda, M. Catalysis Today, Vol. 171, Issue 1, p. 15-23 https://doi.org/10.1016/j.cattod.2011.02.028	journal	August 2011
Oxidative coupling of methane—A complex surface/gas phase mechanism with strong impact on the reaction engineering Beck, Benjamin; Fleischer, Vinzenz; Arndt, Sebastian Catalysis Today, Vol. 228 https://doi.org/10.1016/j.cattod.2013.11.059	journal	June 2014
Oxygen availability and catalytic performance of NaWMn/SiO 2 mixed oxide and its components in oxidative coupling of methane Gordienko, Yury; Usmanov, Timur; Bychkov, Viktor Catalysis Today, Vol. 278 https://doi.org/10.1016/j.cattod.2016.04.021	journal	December 2016
Advances in methane conversion processes Wang, Bingwen; Albarracín-Suazo, Sandra; Pagán-Torres, Yomaira Catalysis Today, Vol. 285 https://doi.org/10.1016/j.cattod.2017.01.023	journal	May 2017
A detailed reaction mechanism for oxidative coupling of methane over Mn/Na2WO4/SiO2 catalyst for non-isothermal conditions Karakaya, Canan; Zhu, Huayang; Loebick, Codruta Catalysis Today, Vol. 312 https://doi.org/10.1016/j.cattod.2018.02.023	journal	August 2018
A single step methane conversion into synthetic fuels using microplasma reactor Nozaki, Tomohiro; Ağıral, Anıl; Yuzawa, Shuhei Chemical Engineering Journal, Vol. 166, Issue 1 https://doi.org/10.1016/j.cej.2010.08.001	journal	January 2011
Micro-kinetic modeling of OCM reactions over Mn/Na2WO4/SiO2 catalyst Sadeghzadeh Ahari, Jafar; Zarrinpashne, Saeed; Sadeghi, Mohammad Taghi Fuel Processing Technology, Vol. 115 https://doi.org/10.1016/j.fuproc.2013.04.006	journal	November 2013
Investigation of the surface reaction network of the oxidative coupling of methane over Na2WO4/Mn/SiO2 catalyst by temperature programmed and dynamic experiments Fleischer, Vinzenz; Steuer, Rolf; Parishan, Samira Journal of Catalysis, Vol. 341 https://doi.org/10.1016/j.jcat.2016.06.014	journal	September 2016
Investigation of the role of the Na2WO4/Mn/SiO2 catalyst composition in the oxidative coupling of methane by chemical looping experiments Fleischer, Vinzenz; Simon, Ulla; Parishan, Samira Journal of Catalysis, Vol. 360 https://doi.org/10.1016/j.jcat.2018.01.022	journal	April 2018
Real-time multi-length scale chemical tomography of fixed bed reactors during the oxidative coupling of methane reaction Vamvakeros, Antonis; Matras, Dorota; Jacques, Simon D. M. Journal of Catalysis, Vol. 386 https://doi.org/10.1016/j.jcat.2020.03.027	journal	June 2020
Correlating Properties of the Mn ₂ O ₃ –Na ₂ WO ₄ /SiO ₂ Catalyst with Statistically Estimated Parameters for the Oxidative Coupling of Methane Huang, Baoting; Hayek, Naseem S.; Sun, Guanjie Energy & Fuels, Vol. 35, Issue 11 https://doi.org/10.1021/acs.energyfuels.1c00481	journal	May 2021
Revisiting Activity- and Selectivity-Enhancing Effects of Water in the Oxidative Coupling of Methane over MnO _x -Na ₂ WO ₄ /SiO ₂ and Proving for Other Materials Aydin, Zeynep; Kondratenko, Vita A.; Lund, Henrik ACS Catalysis, Vol. 10, Issue 15 https://doi.org/10.1021/acscatal.0c01493	journal	July 2020
Elucidating the Effects of Mn Promotion on SiO ₂ -Supported Na-Promoted Tungsten Oxide Catalysts for Oxidative Coupling of Methane (OCM) Kiani, Daniyal; Sourav, Sagar; Baltrusaitis, Jonas ACS Catalysis https://doi.org/10.1021/acscatal.1c01392	journal	July 2021
Resolving the Types and Origin of Active Oxygen Species Present in Supported Mn-Na ₂ WO ₄ /SiO ₂ Catalysts for Oxidative Coupling of Methane Sourav, Sagar; Wang, Yixiao; Kiani, Daniyal ACS Catalysis https://doi.org/10.1021/acscatal.1c02315	journal	August 2021
A Viewpoint on Direct Methane Conversion to Ethane and Ethylene Using Oxidative Coupling on Solid Catalysts Farrell, Brittany Lancaster; Igenegbai, Valentina Omoze; Linic, Suljo ACS Catalysis, Vol. 6, Issue 7 https://doi.org/10.1021/acscatal.6b01087	journal	June 2016
Oxidative Coupling of Methane (OCM) by SiO ₂ -Supported Tungsten Oxide Catalysts Promoted with Mn and Na Kiani, Daniyal; Sourav, Sagar; Baltrusaitis, Jonas ACS Catalysis, Vol. 9, Issue 7 https://doi.org/10.1021/acscatal.9b01585	journal	May 2019
Existence and Properties of Isolated Catalytic Sites on the Surface of β-Cristobalite-Supported, Doped Tungsten Oxide Catalysts (WO _x /β-SiO ₂ , Na-WO _x /β-SiO ₂ , Mn-WO _x /β-SiO ₂ ) for Oxidative Coupling of Methane (OCM): A Combined Periodic DFT and Experimental Study Kiani, Daniyal; Sourav, Sagar; Taifan, William ACS Catalysis, Vol. 10, Issue 8 https://doi.org/10.1021/acscatal.9b05591	journal	March 2020
Site Requirements for the Oxidative Coupling of Methane on SiO ₂ -Supported Mn Catalysts Hou, Sicong; Cao, Yuan; Xiong, Wei Industrial & Engineering Chemistry Research, Vol. 45, Issue 21 https://doi.org/10.1021/ie060269c	journal	October 2006
Oxide/support interaction and surface reconstruction in the sodium tungstate(Na2WO4)/silica system Jiang, Zhi Cheng; Yu, Chang Jiang; Fang, Xue Ping The Journal of Physical Chemistry, Vol. 97, Issue 49 https://doi.org/10.1021/j100151a038	journal	December 1993
Mechanistic Aspects and Reaction Pathways for Oxidative Coupling of Methane on Mn/Na ₂ WO ₄ /SiO ₂ Catalysts Takanabe, Kazuhiro; Iglesia, Enrique The Journal of Physical Chemistry C, Vol. 113, Issue 23 https://doi.org/10.1021/jp9001302	journal	May 2009
Real time chemical imaging of a working catalytic membrane reactor during oxidative coupling of methane Vamvakeros, A.; Jacques, S. D. M.; Middelkoop, V. Chemical Communications, Vol. 51, Issue 64 https://doi.org/10.1039/C5CC03208C	journal	January 2015
Forty years of temporal analysis of products Morgan, K.; Maguire, N.; Fushimi, R. Catalysis Science & Technology, Vol. 7, Issue 12 https://doi.org/10.1039/C7CY00678K	journal	January 2017
Effect of thermal treatment on the stability of Na–Mn–W/SiO ₂ catalyst for the oxidative coupling of methane Matras, Dorota; Vamvakeros, Antonios; Jacques, Simon D. M. Faraday Discussions, Vol. 229 https://doi.org/10.1039/C9FD00142E	journal	January 2021
Methane activation by ZSM-5-supported transition metal centers Kiani, Daniyal; Sourav, Sagar; Tang, Yadan Chemical Society Reviews, Vol. 50, Issue 2 https://doi.org/10.1039/D0CS01016B	journal	January 2021
Synthesis and molecular structure of model silica-supported tungsten oxide catalysts for oxidative coupling of methane (OCM) Kiani, Daniyal; Sourav, Sagar; Wachs, Israel E. Catalysis Science & Technology, Vol. 10, Issue 10 https://doi.org/10.1039/D0CY00289E	journal	January 2020
Methane as raw material in synthetic chemistry: the final frontier Caballero, Ana; Pérez, Pedro J. Chemical Society Reviews, Vol. 42, Issue 23 https://doi.org/10.1039/c3cs60120j	journal	January 2013
Structural analysis of molten Na2WO4 Okada, Kiyoshi; Miyake, Michihiro; Iwai, Shin-ichi Journal of the Chemical Society, Faraday Transactions 2, Vol. 74 https://doi.org/10.1039/f29787401141	journal	January 1978
Structure of the Aqueous Pertechnetate Ion by Raman and Infrared Spectroscopy. Raman and Infrared Spectra of Crystalline KTcO ₄ , KReO ₄ , Na ₂ MoO ₄ , Na ₂ WO ₄ , Na ₂ MoO ₄ ·2H ₂ O, and Na ₂ WO ₄ ·2H ₂ O Busey, R. H.; Keller, O. L. The Journal of Chemical Physics, Vol. 41, Issue 1 https://doi.org/10.1063/1.1725625	journal	July 1964
MnTiO ₃ -driven low-temperature oxidative coupling of methane over TiO ₂ -doped Mn ₂ O ₃ -Na ₂ WO ₄ /SiO ₂ catalyst Wang, Pengwei; Zhao, Guofeng; Wang, Yu Science Advances, Vol. 3, Issue 6 https://doi.org/10.1126/sciadv.1603180	journal	June 2017
Unconventional Chemistry for Unconventional Natural Gas McFarland, E. Science, Vol. 338, Issue 6105 https://doi.org/10.1126/science.1226840	journal	October 2012
Kinetics of the oxidative coupling of methane in the presence of model catalysts Lomonosov, V. I.; Gordienko, Yu. A.; Sinev, M. Yu. Kinetics and Catalysis, Vol. 54, Issue 4 https://doi.org/10.1134/S0023158413040095	journal	July 2013
Thermochemical Properties of the Lattice Oxygen in W,Mn-Containing Mixed Oxide Catalysts for the Oxidative Coupling of Methane Lomonosov, V. I.; Gordienko, Yu. A.; Sinev, M. Yu. Russian Journal of Physical Chemistry A, Vol. 92, Issue 3 https://doi.org/10.1134/S0036024418030147	journal	March 2018

Similar Records

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na ₂ WO ₄ /SiO ₂ Catalysts

Journal Article · Mon Aug 16 00:00:00 EDT 2021 · Angewandte Chemie · OSTI ID:1813634

Molecular structure and catalytic promotional effect of Mn on supported Na₂WO₄/SiO₂ catalysts for oxidative coupling of methane (OCM) reaction

Journal Article · Wed Jul 13 00:00:00 EDT 2022 · Catalysis Today · OSTI ID:2006594

Deciphering the Mechanistic Role of Individual Oxide Phases and Their Combinations in Supported Mn–Na₂WO₄ Catalysts for Oxidative Coupling of Methane

Journal Article · Thu Sep 15 00:00:00 EDT 2022 · ACS Catalysis · OSTI ID:1894589

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts

Citation Formats

References (46)

Similar Records

Related Subjects

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na ₂ WO ₄ /SiO ₂ Catalysts