Density Functional Theory (DFT) Study To Unravel the Catalytic Properties of M-Exchanged MFI, (M = Be, Co, Cu, Mg, Mn, Zn) for the Conversion of Methane and Carbon Dioxide to Acetic Acid

Montejo-Valencia, Brian D.; Pagán-Torres, Yomaira J.; Martínez-Iñesta, María M.; Curet-Arana, María C.

doi:10.1021/acscatal.7b00844

Title: Density Functional Theory (DFT) Study To Unravel the Catalytic Properties of M-Exchanged MFI, (M = Be, Co, Cu, Mg, Mn, Zn) for the Conversion of Methane and Carbon Dioxide to Acetic Acid

Journal Article · Wed Sep 06 00:00:00 EDT 2017 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b00844· OSTI ID:1485301

Montejo-Valencia, Brian D. ^[1]; Pagán-Torres, Yomaira J. ^[1]; Martínez-Iñesta, María M. ^[1];

^[1]

Univ. of Puerto Rico, Mayaguez (Puerto Rico). Dept. of Chemical Engineering

The conversion of greenhouse gases, such as CO₂ and CH₄, to value chemicals is a major challenge, because of the high stability of both molecules. In this study, density functional theory (DFT) calculations with long-range corrections and ONIOM were used to analyze the reaction mechanism for the conversion of CO₂ and CH₄ to acetic acid with MFI zeolite exchanged with Be, Co, Cu, Mg, Mn, and Zn cations. Our results demonstrate that (a) the highest reaction barrier on the reaction mechanism is CH₄ dissociation, and the transition state energy in that step is directly related to the energy of the lowest unoccupied molecular orbital and the electronegativity of the metal exchanged zeolites; (b) a charge transfer between CH₄ and the metal cation occurs simultaneously to CH₄ dissociation; (c) CO₂ insertion has a low energy barrier, and the protonation of the acetate species is spontaneous; (d) dispersion interactions are the main contributions to CH₄ adsorption energies, whereas, in the rest of the steps of the reaction mechanism, the contribution of dispersion to the energies of reaction is almost negligible; (e) desorption of acetic acid could be promoted by the coadsorption of water; and (f) CH₄ dissociation on Cu-MFI has an apparent activation energy of 11.5 kcal/mol, and a forward rate constant of 1.1 s–1 at 398 K.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1485301

Journal Information:: ACS Catalysis, Vol. 7, Issue 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 47 works

Citation information provided by
Web of Science

References (55)

Unconventional Chemistry for Unconventional Natural Gas McFarland, E. Science, Vol. 338, Issue 6105 https://doi.org/10.1126/science.1226840	journal	October 2012
Conversion of Methane and Carbon Dioxide to Higher Value Products Havran, Vesna; Duduković, Milorad P.; Lo, Cynthia S. Industrial & Engineering Chemistry Research, Vol. 50, Issue 12 https://doi.org/10.1021/ie2000192	journal	June 2011
Understanding and exploiting C–H bond activation Labinger, Jay A.; Bercaw, John E. Nature, Vol. 417, Issue 6888 https://doi.org/10.1038/417507a	journal	May 2002
Strategies for the Direct Catalytic Valorization of Methane Using Heterogeneous Catalysis: Challenges and Opportunities Olivos-Suarez, Alma I.; Szécsényi, Àgnes; Hensen, Emiel J. M. ACS Catalysis, Vol. 6, Issue 5 https://doi.org/10.1021/acscatal.6b00428	journal	April 2016
CH 4 conversion to value added products: Potential, limitations and extensions of a single step heterogeneous catalysis Taifan, William; Baltrusaitis, Jonas Applied Catalysis B: Environmental, Vol. 198 https://doi.org/10.1016/j.apcatb.2016.05.081	journal	December 2016
Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature Narsimhan, Karthik; Iyoki, Kenta; Dinh, Kimberly ACS Central Science, Vol. 2, Issue 6 https://doi.org/10.1021/acscentsci.6b00139	journal	April 2016
Monocopper Active Site for Partial Methane Oxidation in Cu-Exchanged 8MR Zeolites Kulkarni, Ambarish R.; Zhao, Zhi-Jian; Siahrostami, Samira ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01895	journal	September 2016
Reaction Conditions of Methane-to-Methanol Conversion Affect the Structure of Active Copper Sites Alayon, Evalyn Mae C.; Nachtegaal, Maarten; Bodi, Andras ACS Catalysis, Vol. 4, Issue 1 https://doi.org/10.1021/cs400713c	journal	December 2013
Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol Grundner, Sebastian; Markovits, Monica A. C.; Li, Guanna Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8546	journal	June 2015
Isothermal Cyclic Conversion of Methane into Methanol over Copper-Exchanged Zeolite at Low Temperature Tomkins, Patrick; Mansouri, Ali; Bozbag, Selmi E. Angewandte Chemie International Edition, Vol. 55, Issue 18 https://doi.org/10.1002/anie.201511065	journal	March 2016
A [Cu ₂ O] ²⁺ core in Cu-ZSM-5, the active site in the oxidation of methane to methanol Woertink, Julia S.; Smeets, Pieter J.; Groothaert, Marijke H. Proceedings of the National Academy of Sciences, Vol. 106, Issue 45 https://doi.org/10.1073/pnas.0910461106	journal	October 2009
Conversion of methane to methanol on copper-containing small-pore zeolites and zeotypes Wulfers, M. J.; Teketel, S.; Ipek, B. Chemical Communications, Vol. 51, Issue 21 https://doi.org/10.1039/C4CC09645B	journal	January 2015
Selective Oxidation of Methane by the Bis(μ-oxo)dicopper Core Stabilized on ZSM-5 and Mordenite Zeolites Groothaert, Marijke H.; Smeets, Pieter J.; Sels, Bert F. Journal of the American Chemical Society, Vol. 127, Issue 5 https://doi.org/10.1021/ja047158u	journal	February 2005
Spectroscopic Definition of the Copper Active Sites in Mordenite: Selective Methane Oxidation Vanelderen, Pieter; Snyder, Benjamin E. R.; Tsai, Ming-Li Journal of the American Chemical Society, Vol. 137, Issue 19 https://doi.org/10.1021/jacs.5b02817	journal	May 2015
Theoretical Insights into the Selective Oxidation of Methane to Methanol in Copper-Exchanged Mordenite Zhao, Zhi-Jian; Kulkarni, Ambarish; Vilella, Laia ACS Catalysis, Vol. 6, Issue 6 https://doi.org/10.1021/acscatal.6b00440	journal	May 2016
Computationally Exploring Confinement Effects in the Methane-to-Methanol Conversion Over Iron-Oxo Centers in Zeolites Göltl, Florian; Michel, Carine; Andrikopoulos, Prokopis C. ACS Catalysis, Vol. 6, Issue 12 https://doi.org/10.1021/acscatal.6b02640	journal	November 2016
Theoretical Investigation of the Selective Oxidation of Methane to Methanol on Nanostructured Fe-ZSM-5 by the ONIOM Method Pantu, Piboon; Pabchanda, Suwat; Limtrakul, Jumras ChemPhysChem, Vol. 5, Issue 12 https://doi.org/10.1002/cphc.200400156	journal	December 2004
Direct Conversion of Methane to Methanol by Metal-Exchanged ZSM-5 Zeolite (Metal = Fe, Co, Ni, Cu) Mahyuddin, M. Haris; Staykov, Aleksandar; Shiota, Yoshihito ACS Catalysis, Vol. 6, Issue 12 https://doi.org/10.1021/acscatal.6b01721	journal	November 2016
Carboxylation of methane with CO or CO2 in aqueous solution catalysed by vanadium complexes Nizova, Galina V.; Shul’pin, Georgiy B.; Nizova, Galina V. Chemical Communications, Issue 17 https://doi.org/10.1039/a804699i	journal	January 1998
Palladium-Catalyzed Acetic Acid Synthesis from Methane and Carbon Monoxide or Dioxide Kurioka, Masanobu; Nakata, Kazuyuki; Jintoku, Tetsuro Chemistry Letters, Vol. 24, Issue 3 https://doi.org/10.1246/cl.1995.244	journal	March 1995
Possibility of Direct Conversion of CH4 and CO2 to High-Value Products Huang, W.; Xie, K. -C; Wang, J. -P Journal of Catalysis, Vol. 201, Issue 1 https://doi.org/10.1006/jcat.2001.3223	journal	July 2001
Direct synthesis of acetic acid from CH4 and CO2 by a step-wise route over Pd/SiO2 and Rh/SiO2 catalysts Ding, Yi-Hui; Huang, Wei; Wang, Yong-Gang Fuel Processing Technology, Vol. 88, Issue 4 https://doi.org/10.1016/j.fuproc.2004.09.003	journal	April 2007
Direct catalytic formation of acetic acid from CO2 and methane Wilcox, Esther M.; Roberts, George W.; Spivey, James J. Catalysis Today, Vol. 88, Issue 1-2 https://doi.org/10.1016/j.cattod.2003.08.007	journal	December 2003
Methane to Acetic Acid over Cu-Exchanged Zeolites: Mechanistic Insights from a Site-Specific Carbonylation Reaction Narsimhan, Karthik; Michaelis, Vladimir K.; Mathies, Guinevere Journal of the American Chemical Society, Vol. 137, Issue 5 https://doi.org/10.1021/ja5106927	journal	January 2015
Mechanistic Insight into the Formation of Acetic Acid from the Direct Conversion of Methane and Carbon Dioxide on Zinc-Modified H–ZSM-5 Zeolite Wu, Jian-Feng; Yu, Si-Min; Wang, Wei David Journal of the American Chemical Society, Vol. 135, Issue 36 https://doi.org/10.1021/ja406978q	journal	August 2013
Direct synthesis of acetic acid by simultaneous co-activation of methane and CO2 over Cu-exchanged ZSM-5 catalysts Rabie, Abdelrahman M.; Betiha, Mohamed A.; Park, Sang-Eon Applied Catalysis B: Environmental, Vol. 215 https://doi.org/10.1016/j.apcatb.2017.05.053	journal	October 2017
NMR-Spectroscopic Evidence of Intermediate-Dependent Pathways for Acetic Acid Formation from Methane and Carbon Monoxide over a ZnZSM-5 Zeolite Catalyst Wang, Xiumei; Qi, Guodong; Xu, Jun Angewandte Chemie International Edition, Vol. 51, Issue 16 https://doi.org/10.1002/anie.201108634	journal	March 2012
Reactivity of C1 Surface Species Formed in Methane Activation on Zn-Modified H-ZSM-5 Zeolite Wu, Jian Feng; Wang, Wei David; Xu, Jun Chemistry - A European Journal, Vol. 16, Issue 47 https://doi.org/10.1002/chem.201002258	journal	October 2010
Electronic Structure of Zn ⁺ -Modified Zeolite: A Density Functional Theory Study of Ferrierite Benco, Lubomir The Journal of Physical Chemistry C, Vol. 120, Issue 11 https://doi.org/10.1021/acs.jpcc.5b12079	journal	March 2016
Direct C–C Coupling of CO ₂ and the Methyl Group from CH ₄ Activation through Facile Insertion of CO ₂ into Zn–CH ₃ σ-Bond Zhao, Yuntao; Cui, Chaonan; Han, Jinyu Journal of the American Chemical Society, Vol. 138, Issue 32 https://doi.org/10.1021/jacs.6b04446	journal	August 2016
The conversion of CO2 and CH4 to acetic acid over the Au-exchanged ZSM-5 catalyst: a density functional theory study Panjan, Wasinee; Sirijaraensre, Jakkapan; Warakulwit, Chompunuch Physical Chemistry Chemical Physics, Vol. 14, Issue 48 https://doi.org/10.1039/c2cp42066j	journal	January 2012
Mechanism of CH ₄ Activation on a Monomeric Zn ²⁺ -Ion Exchanged in MFI-Type Zeolite with a Specific Al Arrangement: Similarity to the Activation Site for H ₂ Oda, Akira; Torigoe, Hiroe; Itadani, Atsushi The Journal of Physical Chemistry C https://doi.org/10.1021/jp4065517	journal	September 2013
An Important Factor in CH ₄ Activation by Zn Ion in Comparison with Mg Ion in MFI: The Superior Electron-Accepting Nature of Zn ²⁺ Oda, Akira; Torigoe, Hiroe; Itadani, Atsushi The Journal of Physical Chemistry C, Vol. 118, Issue 28 https://doi.org/10.1021/jp5013413	journal	July 2014
Identification of Cu(ii) coordination structures in Cu-ZSM-5, based on a DFT/ab initio assignment of the EPR spectra Groothaert, Marijke H.; Pierloot, Kristine; Delabie, Annelies Physical Chemistry Chemical Physics, Vol. 5, Issue 10 https://doi.org/10.1039/b301120h	journal	January 2003
Co2+ ion siting in pentasil-containing zeolites, part 3. Dědeček, J.; Kaucký, D.; Wichterlová, B. Microporous and Mesoporous Materials, Vol. 35-36 https://doi.org/10.1016/S1387-1811(99)00244-9	journal	April 2000
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections Chai, Jeng-Da; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 10, Issue 44 https://doi.org/10.1039/b810189b	journal	January 2008
The path of chemical reactions - the IRC approach Fukui, Kenichi Accounts of Chemical Research, Vol. 14, Issue 12 https://doi.org/10.1021/ar00072a001	journal	December 1981
The IMOMO method: Integration of different levels of molecular orbital approximations for geometry optimization of large systems: Test for n ‐butane conformation and S _N 2 reaction: RCl+Cl ⁻ Humbel, Stéphane; Sieber, Stefan; Morokuma, Keiji The Journal of Chemical Physics, Vol. 105, Issue 5 https://doi.org/10.1063/1.472065	journal	August 1996
UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations Rappe, A. K.; Casewit, C. J.; Colwell, K. S. Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035 https://doi.org/10.1021/ja00051a040	journal	December 1992
QM/MM Study on the Catalytic Mechanism of Benzene Hydroxylation over Fe−ZSM-5 Shiota, Yoshihito; Suzuki, Kunihiko; Yoshizawa, Kazunari Organometallics, Vol. 25, Issue 13 https://doi.org/10.1021/om0509591	journal	June 2006
Skeletal Isomerization of 1-Butene over Ferrierite Zeolite: A Quantum Chemical Analysis of Structures and Reaction Mechanisms Wattanakit, Chularat; Nokbin, Somkiat; Boekfa, Bundet The Journal of Physical Chemistry C, Vol. 116, Issue 9 https://doi.org/10.1021/jp209991y	journal	February 2012
HCl Adsorption on Copper-Modified ZSM-5: FTIR and DFT Study Mosallanejad, Sara; Dlugogorski, Bogdan Z.; Kennedy, Eric M. The Journal of Physical Chemistry C https://doi.org/10.1021/jp3122243	journal	September 2013
Mechanistic Investigation on 1,5- to 2,6-Dimethylnaphthalene Isomerization Catalyzed by Acidic β Zeolite: ONIOM Study with an M06-L Functional Kumsapaya, Chawanwit; Bobuatong, Karan; Khongpracha, Pipat The Journal of Physical Chemistry C, Vol. 113, Issue 36 https://doi.org/10.1021/jp904098t	journal	August 2009
Incorporation of Co(II) in Dealuminated BEA Zeolite at Lattice Tetrahedral Sites Evidenced by XRD, FTIR, Diffuse Reflectance UV−Vis, EPR, and TPR Dzwigaj, S.; Che, M. The Journal of Physical Chemistry B, Vol. 110, Issue 25 https://doi.org/10.1021/jp0623387	journal	June 2006
EPR spectroscopy of copper and manganese complexes encapsulated in zeolites Bennur, T. H.; Srinivas, D.; Ratnasamy, Paul Microporous and Mesoporous Materials, Vol. 48, Issue 1-3 https://doi.org/10.1016/S1387-1811(01)00345-6	journal	November 2001
Potential for C−H Activation in CH ₄ Utilizing a CuMFI-Type Zeolite as a Catalyst Itadani, Atsushi; Sugiyama, Hiroyuki; Tanaka, Masashi The Journal of Physical Chemistry C, Vol. 113, Issue 17 https://doi.org/10.1021/jp807008t	journal	April 2009
DRIFT study of molecular and dissociative adsorption of light paraffins by HZSM-5 zeolite modified with zinc ions: methane adsorption Kazansky, V. Journal of Catalysis, Vol. 225, Issue 2 https://doi.org/10.1016/j.jcat.2004.04.029	journal	July 2004
The Solid-State Structures of Dimethylzinc and Diethylzinc Bacsa, John; Hanke, Felix; Hindley, Sarah Angewandte Chemie, Vol. 123, Issue 49 https://doi.org/10.1002/ange.201105099	journal	September 2011
Structure and Reactivity of Zn-Modified ZSM-5 Zeolites: The Importance of Clustered Cationic Zn Complexes Almutairi, Sami M. T.; Mezari, Brahim; Magusin, Pieter C. M. M. ACS Catalysis, Vol. 2, Issue 1 https://doi.org/10.1021/cs200441e	journal	December 2011
Absolute electronegativity and hardness correlated with molecular orbital theory Pearson, R. G. Proceedings of the National Academy of Sciences, Vol. 83, Issue 22 https://doi.org/10.1073/pnas.83.22.8440	journal	November 1986
The interaction mechanism of CO2 with CH3 and H on Cu (111) surface in synthesis of acetic acid from CH4/CO2: A DFT study Zhang, Riguang; Song, Luzhi; Liu, Hongyan Applied Catalysis A: General, Vol. 443-444 https://doi.org/10.1016/j.apcata.2012.07.024	journal	November 2012
Insertion of Carbon Dioxide into (PCP)Pd ^II −Me Bonds Johansson, Roger; Jarenmark, Martin; Wendt, Ola F. Organometallics, Vol. 24, Issue 19 https://doi.org/10.1021/om0505561	journal	August 2005
Exploring the reactions of CO ₂ with PCP supported nickel complexes Schmeier, Timothy J.; Hazari, Nilay; Incarvito, Christopher D. Chem. Commun., Vol. 47, Issue 6 https://doi.org/10.1039/C0CC03898A	journal	January 2011
Ab initio MO study of carbon dioxide insertion into a copper(I)-hydrogen bond. Semiquantitative understanding of changes in geometry, bonding, and electron distribution during the reaction Sakaki, Shigeyoshi; Ohkubo, Katsutoshi Inorganic Chemistry, Vol. 28, Issue 13 https://doi.org/10.1021/ic00312a016	journal	June 1989
Mechanisms of the CO ₂ Insertion into (PCP) Palladium Allyl and Methyl σ-Bonds. A Kinetic and Computational Study Johnson, Magnus T.; Johansson, Roger; Kondrashov, Mikhail V. Organometallics, Vol. 29, Issue 16 https://doi.org/10.1021/om100325v	journal	August 2010

Cited By (11)

Coupling of Methane and Carbon Dioxide Mediated by Diatomic Copper Boride Cations Chen, Qiang; Zhao, Yan-Xia; Jiang, Li-Xue Angewandte Chemie International Edition, Vol. 57, Issue 43 https://doi.org/10.1002/anie.201808780	journal	October 2018
Computational screening of metal-substituted HKUST-1 catalysts for chemical fixation of carbon dioxide into epoxides Hu, Tian-ding; Jiang, Yan; Ding, Yi-hong Journal of Materials Chemistry A, Vol. 7, Issue 24 https://doi.org/10.1039/c9ta02455g	journal	January 2019
Direct Conversion of Methane with Carbon Dioxide Mediated by RhVO ₃ ⁻ Cluster Anions Yang, Yuan; Yang, Bin; Zhao, Yan‐Xia Angewandte Chemie, Vol. 131, Issue 48 https://doi.org/10.1002/ange.201911195	journal	November 2019
Monitoring spatio-temporal dynamics of urban and peri-urban land transitions using ensemble of remote sensing spectral indices—a case study of Chennai Metropolitan Area, India M., Mathan; M., Krishnaveni Environmental Monitoring and Assessment, Vol. 192, Issue 1 https://doi.org/10.1007/s10661-019-7986-y	journal	December 2019
Direct Conversion of Methane with Carbon Dioxide Mediated by RhVO ₃ ⁻ Cluster Anions Yang, Yuan; Yang, Bin; Zhao, Yan‐Xia Angewandte Chemie International Edition, Vol. 58, Issue 48 https://doi.org/10.1002/anie.201911195	journal	November 2019
Direct synthesis of acetic acid from carbon dioxide and methane over Cu-modulated BEA, MFI, MOR and TON zeolites: a density functional theory study Wang, Sen; Guo, Shujia; Luo, Yaoya Catalysis Science & Technology, Vol. 9, Issue 23 https://doi.org/10.1039/c9cy01803d	journal	January 2019
Mechanistic insights into the catalytic role of various acid sites on ZSM-5 zeolite in the carbonylation of methanol and dimethyl ether Wang, Sen; Li, Shiying; Zhang, Li Catalysis Science & Technology, Vol. 8, Issue 12 https://doi.org/10.1039/c8cy00296g	journal	January 2018
The Nature and Catalytic Function of Cation Sites in Zeolites: a Computational Perspective Li, Guanna; Pidko, Evgeny A. ChemCatChem, Vol. 11, Issue 1 https://doi.org/10.1002/cctc.201801493	journal	October 2018
Ionic liquids tailored and confined by one-step assembly with mesoporous silica for boosting the catalytic conversion of CO ₂ into cyclic carbonates Su, Qian; Qi, Yaqiong; Yao, Xiaoqian Green Chemistry, Vol. 20, Issue 14 https://doi.org/10.1039/c8gc01038b	journal	January 2018
Coupling of Methane and Carbon Dioxide Mediated by Diatomic Copper Boride Cations Chen, Qiang; Zhao, Yan-Xia; Jiang, Li-Xue Angewandte Chemie, Vol. 130, Issue 43 https://doi.org/10.1002/ange.201808780	journal	October 2018
C−H Bond Carboxylation with Carbon Dioxide Hong, Junting; Li, Man; Zhang, Jianning ChemSusChem, Vol. 12, Issue 1 https://doi.org/10.1002/cssc.201802012	journal	December 2018

Similar Records

Highly Selective H2 Separation Zeolite Membranes for Coal Gasification Membrane Reactor Applications

Technical Report · Sun Sep 24 00:00:00 EDT 2006 · OSTI ID:1485301

Hong, Mei; Noble, Richard D; Falconer, John L

Computational Modeling of the Nature and Role of Ga Species for Light Alkane Dehydrogenation Catalyzed by Ga/H-MFI

Journal Article · Tue May 15 00:00:00 EDT 2018 · ACS Catalysis · OSTI ID:1485301

Mansoor, Erum; Head-Gordon, Martin; Bell, Alexis T.

Computational Design of Metal-Exchanged MFI Zeolites for Coupling CO₂–Ethylene to Form Acrylic Acid

Journal Article · Fri Mar 22 00:00:00 EDT 2024 · ACS Sustainable Chemistry & Engineering · OSTI ID:1485301

Masood, Zaheer; Nguyen, Quy P.; Wang, Bin

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Density Functional Theory (DFT) Study To Unravel the Catalytic Properties of M-Exchanged MFI, (M = Be, Co, Cu, Mg, Mn, Zn) for the Conversion of Methane and Carbon Dioxide to Acetic Acid

Citation Formats

References (55)

Cited By (11)

Similar Records

Related Subjects