Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites

Jones, Andrew J.; Iglesia, Enrique

doi:10.1002/anie.201406823

Cited by 142Zeolite Catalysis and SynthesisCatalysis and Oxidation ReactionsChemical Synthesis and Reactions

Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites

Jones, Andrew J., Iglesia, Enrique·2014·Angewandte Chemie International Edition

DOI 10.1002/anie.201406823

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Abstract

Mechanistic interpretations of rates and in situ IR spectra combined with density functionals that account for van der Waals interactions of intermediates and transition states within confining voids show that associative routes mediate the formation of dimethyl ether from methanol on zeolitic acids at the temperatures and pressures of practical dehydration catalysis. Methoxy‐mediated dissociative routes become prevalent at higher temperatures and lower pressures, because they involve smaller transition states with higher enthalpy, but also higher entropy, than those in associative routes. These enthalpy–entropy trade‐offs merely reflect the intervening role of temperature in activation free energies and the prevalence of more complex transition states at low temperatures and high pressures. This work provides a foundation for further inquiry into the contributions of H‐bonded methanol and methoxy species in homologation and hydrocarbon synthesis reactions from methanol.

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At Brønsted acid sites, DME can be formed via a concerted and a stepwise mechanism.
“AtBrønstedacidsites,DMEcanbeformedviatheconcertedandthestepwisemechanism.”
From Reactivity of Surface Lewis and Brønsted Acid Sites in Zeolite Catalysis: A Computational Case Study of DME Synthesis Using H-SSZ-13 (2022) · cites this paper as [76]
Due to the higher entropic penalty of the concerted mechanism, the stepwise mechanism typically contributes more to the overall reaction rate at higher temperatures.
“Duetothehigherentropicpenaltyofthe concertedmechanism,thestepwisemechanismtypically contributesmoretotheoverallreactionrateathighertemperatures. 19,76,104”
From Reactivity of Surface Lewis and Brønsted Acid Sites in Zeolite Catalysis: A Computational Case Study of DME Synthesis Using H-SSZ-13 (2022) · cites this paper as [76]
In the concerted mechanism, two adsorbed MeOH react directly.
“Intheconcertedmechanism,twoadsorbedMeOH reactdirectly.”
From Reactivity of Surface Lewis and Brønsted Acid Sites in Zeolite Catalysis: A Computational Case Study of DME Synthesis Using H-SSZ-13 (2022) · cites this paper as [76]
The calculations suggest that the stepwise mechanism dominates at these reaction conditions.
“Ourcalculationsthussuggestthatthestepwisemechanismdominates atthesereactionconditions,inlinewithearliertheoretical work. 76,104”
From Reactivity of Surface Lewis and Brønsted Acid Sites in Zeolite Catalysis: A Computational Case Study of DME Synthesis Using H-SSZ-13 (2022) · cites this paper as [76]
In the stepwise mechanism, DME is formed through reaction of a surface methoxyspecies (SMS) with MeOH.
“Inthestepwisemechanism,DMEisformed throughreactionofasurfacemethoxyspecies(SMS)with MeOH.”
From Reactivity of Surface Lewis and Brønsted Acid Sites in Zeolite Catalysis: A Computational Case Study of DME Synthesis Using H-SSZ-13 (2022) · cites this paper as [76]

Efficient iterative schemes for <i>ab initio</i> total-energy calculations using a plane-wave basis set
Kresse, G., & Furthmüller, J. (1996) · Physical Review B · doi:10.1103/physrevb.54.11169 · Cited by 123,652 · see citing works
Projector augmented-wave method
Blöchl, P. E. (1994) · Physical Review B · doi:10.1103/physrevb.50.17953 · Cited by 92,732 · see citing works
From ultrasoft pseudopotentials to the projector augmented-wave method
Kresse, G., & Joubert, D. (1999) · Physical Review B · doi:10.1103/physrevb.59.1758 · Cited by 85,307 · see citing works
Ab initio molecular dynamics for liquid metals
Kresse, G., & Häfner, J. (1993) · Physical review. B, Condensed matter · doi:10.1103/physrevb.47.558 · Cited by 45,654 · see citing works
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
Henkelman, G., & Jónsson, H. (2000) · The Journal of Chemical Physics · doi:10.1063/1.1323224 · Cited by 9,496 · see citing works
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
Henkelman, G., & Jónsson, H. (1999) · The Journal of Chemical Physics · doi:10.1063/1.480097 · Cited by 3,558 · see citing works
Higher-accuracy van der Waals density functional
Lee, K., Murray, É., Kong, L., Lundqvist, B. I., & Langreth, D. C. (2010) · Physical Review B · doi:10.1103/physrevb.82.081101 · Cited by 2,765 · see citing works
Conversion of Methanol to Hydrocarbons: How Zeolite Cavity and Pore Size Controls Product Selectivity
Olsbye, U., Svelle, S., Bjørgen, M., Beato, P., Janssens, T. V. W., Joensen, F., Bordiga, S., & Lillerud, K. P. (2012) · Angewandte Chemie International Edition · doi:10.1002/anie.201103657 · Cited by 1,809 · see citing works
Methanol-to-hydrocarbons: catalytic materials and their behavior
Stöcker, M. (1999) · Microporous and Mesoporous Materials · doi:10.1016/s1387-1811(98)00319-9 · Cited by 1,478 · see citing works
Acidity Differences between Inorganic Solids Induced by Their Framework Structure. A Combined Quantum Mechanics/Molecular Mechanics ab Initio Study on Zeolites
Brändle, M. P., & Sauer, J. (1998) · Journal of the American Chemical Society · doi:10.1021/ja9729037 · Cited by 380 · see citing works
Reactivity of Surface Alkoxy Species on Acidic Zeolite Catalysts
Wang, W., & Hunger, M. (2008) · Accounts of Chemical Research · doi:10.1021/ar700210f · Cited by 268 · see citing works
Acid strength and solvation in catalysis by MFI zeolites and effects of the identity, concentration and location of framework heteroatoms
Jones, A., Carr, R. T., Zones, S. I., & Enrique Iglesia, A. (2014) · Journal of Catalysis · doi:10.1016/j.jcat.2014.01.007 · Cited by 265 · see citing works
Self-citation
Evidence for an Initiation of the Methanol-to-Olefin Process by Reactive Surface Methoxy Groups on Acidic Zeolite Catalysts
Wang, W., Buchholz, A., Seiler, M., & Hunger, M. (2003) · Journal of the American Chemical Society · doi:10.1021/ja0304244 · Cited by 263 · see citing works
The Roles of Entropy and Enthalpy in Stabilizing Ion-Pairs at Transition States in Zeolite Acid Catalysis
Gounder, R., & Enrique Iglesia, A. (2011) · Accounts of Chemical Research · doi:10.1021/ar200138n · Cited by 249 · see citing works
Self-citation
The Mechanism of Dimethyl Ether Formation from Methanol Catalyzed by Zeolitic Protons
Blaszkowski, S. R., & van Santen, R. A. (1996) · Journal of the American Chemical Society · doi:10.1021/ja954323k · Cited by 227 · see citing works
Catalytic consequences of acid strength in the conversion of methanol to dimethyl ether
Carr, R. T., Neurock, M., & Iglesia, E. (2011) · Journal of Catalysis · doi:10.1016/j.jcat.2010.11.017 · Cited by 203 · see citing works
Theoretical Study of the Mechanism of Surface Methoxy and Dimethyl Ether Formation from Methanol Catalyzed by Zeolitic Protons
Blaszkowski, S. R., & van Santen, R. A. (1997) · The Journal of Physical Chemistry B · doi:10.1021/jp962006+ · Cited by 181 · see citing works
Umwandlung von Methanol in Kohlenwasserstoffe: Wie Zeolith‐Hohlräume und Porengröße die Produktselektivität bestimmen
Olsbye, U., Svelle, S., Bjørgen, M., Beato, P., Janssens, T. V. W., Joensen, F., Bordiga, S., & Lillerud, K. P. (2012) · Angewandte Chemie · doi:10.1002/ange.201103657 · Cited by 159 · see citing works
Implications of Transition State Confinement within Small Voids for Acid Catalysis
Jones, A., Zones, S. I., & Enrique Iglesia, A. (2014) · The Journal of Physical Chemistry C · doi:10.1021/jp5050095 · Cited by 146 · see citing works
Self-citation
Van der Waals interactions between hydrocarbon molecules and zeolites: Periodic calculations at different levels of theory, from density functional theory to the random phase approximation and Møller-Plesset perturbation theory
Göltl, F., Grüneis, A., Bučko, T., & Häfner, J. (2012) · The Journal of Chemical Physics · doi:10.1063/1.4750979 · Cited by 144 · see citing works
IR spectroscopy of neutral and ionic hydrogen-bonded complexes formed upon interaction of CH 3 OH, C 2 H 5 OH, (CH 3 ) 2 O, (C 2 H 5 ) 2 O and C 4 H 8 O with H-Y, H-ZSM-5 and H-mordenite: comparison with analogous adducts formed on the H-Nafion superacidic membrane
Zecchina, A., Bordiga, S., Spoto, G., Scarano, D., Spanò, G., & Geobaldo, F. (1996) · Journal of the Chemical Society Faraday Transactions · doi:10.1039/ft9969204863 · Cited by 128 · see citing works
Monomolecular cracking of propane over acidic chabazite: An ab initio molecular dynamics and transition path sampling study
Bučko, T., Benco, Ľ., Häfner, J., & Ángyán, J. G. (2011) · Journal of Catalysis · doi:10.1016/j.jcat.2011.01.022 · Cited by 112 · see citing works
Evidence for a “Carbene‐like” Intermediate during the Reaction of Methoxy Species with Light Alkenes on H‐ZSM‐5
Yamazaki, H., Shima, H., Imai, H., Yokoi, T., Tatsumi, T., & Kondo, J. N. (2011) · Angewandte Chemie International Edition · doi:10.1002/anie.201007178 · Cited by 108 · see citing works
Methanol to Dimethyl Ether over ZSM-22: A Periodic Density Functional Theory Study
Moses, P. G., & Nørskov, J. K. (2013) · ACS Catalysis · doi:10.1021/cs300722w · Cited by 94 · see citing works
Surface reactivity of zeolites type H-Y and Na-Y with methanol
Salvador, P., & Kladnig, W. F. (1977) · Journal of the Chemical Society Faraday Transactions 1 Physical Chemistry in Condensed Phases · doi:10.1039/f19777301153 · Cited by 87 · see citing works
Direct Production of Propene from Methoxy Species and Dimethyl Ether over H-ZSM-5
Yamazaki, H., Shima, H., Imai, H., Yokoi, T., Tatsumi, T., & Kondo, J. N. (2012) · The Journal of Physical Chemistry C · doi:10.1021/jp307290z · Cited by 83 · see citing works
Entropy effects in hydrocarbon conversion reactions: free-energy integrations and transition-path sampling
Bučko, T., & Häfner, J. (2010) · Journal of Physics Condensed Matter · doi:10.1088/0953-8984/22/38/384201 · Cited by 35 · see citing works
Evidence for a “Carbene‐like” Intermediate during the Reaction of Methoxy Species with Light Alkenes on H‐ZSM‐5
Yamazaki, H., Shima, H., Imai, H., Yokoi, T., Tatsumi, T., & Kondo, J. N. (2011) · Angewandte Chemie · doi:10.1002/ange.201007178 · Cited by 21 · see citing works

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Speybroeck, V. V., Hemelsoet, K., Joos, L., Waroquier, M., Bell, R. G., & Catlow, C. R. A. (2015) · Chemical Society Reviews · doi:10.1039/c5cs00029g · Cited by 516 · see citing works
The Strength of Brønsted Acid Sites in Microporous Aluminosilicates
Jones, A., & Enrique Iglesia, A. (2015) · ACS Catalysis · doi:10.1021/acscatal.5b01133 · Cited by 269 · see citing works
Self-citation
Molecular Views on Mechanisms of Brønsted Acid-Catalyzed Reactions in Zeolites
Chizallet, C., Bouchy, C., Larmier, K., & Pirngruber, G. D. (2023) · Chemical Reviews · doi:10.1021/acs.chemrev.2c00896 · Cited by 256 · see citing works
Selective Introduction of Acid Sites in Different Confined Positions in ZSM-5 and Its Catalytic Implications
Li, C., Vidal‐Moya, A., Miguel, P. J., Dědeček, J., Boronat, M., & Corma, A. (2018) · ACS Catalysis · doi:10.1021/acscatal.8b02112 · Cited by 230 · see citing works
Consideration of the Aluminum Distribution in Zeolites in Theoretical and Experimental Catalysis Research
Knott, B. C., Nimlos, C. T., Robichaud, D. J., Nimlos, M. R., Kim, S., & Gounder, R. (2017) · ACS Catalysis · doi:10.1021/acscatal.7b03676 · Cited by 221 · see citing works
Confinement effects and acid strength in zeolites
Grifoni, E., Piccini, G., Lercher, J. A., Glezakou, V.-A., Rousseau, R., & Parrinello, M. (2021) · Nature Communications · doi:10.1038/s41467-021-22936-0 · Cited by 203 · see citing works
Introducing Catalytic Diversity into Single-Site Chabazite Zeolites of Fixed Composition via Synthetic Control of Active Site Proximity
Iorio, J. R. D., Nimlos, C. T., & Gounder, R. (2017) · ACS Catalysis · doi:10.1021/acscatal.7b01273 · Cited by 157 · see citing works
Unraveling the Mechanism of the Initiation Reaction of the Methanol to Olefins Process Using ab Initio and DFT Calculations
Pleßow, P. N., & Studt, F. (2017) · ACS Catalysis · doi:10.1021/acscatal.7b03114 · Cited by 157 · see citing works
On the Redox Mechanism of Low‐Temperature NH3‐SCR over Cu‐CHA: A Combined Experimental and Theoretical Study of the Reduction Half Cycle
Hu, W., Selleri, T., Gramigni, F., Fenes, E., Rout, K. R., Liu, S., Nova, I., Chen, D., Gao, X., & Tronconi, E. (2021) · Angewandte Chemie International Edition · doi:10.1002/anie.202014926 · Cited by 157 · see citing works
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Wang, A., Chen, Y., Walter, É., Washton, N., Mei, D., Varga, T. R., Wang, Y., Szanyi, J., Wang, Y., Peden, C. H. F., et al. (2019) · Nature Communications · doi:10.1038/s41467-019-09021-3 · Cited by 148 · see citing works
Dehydration Pathways of 1-Propanol on HZSM-5 in the Presence and Absence of Water
Zhi, Y., Shi, H., Mu, L., Liu, Y., Mei, D., Camaioni, D. M., & Lercher, J. A. (2015) · Journal of the American Chemical Society · doi:10.1021/jacs.5b09107 · Cited by 142 · see citing works
Steric Effect and Evolution of Surface Species in the Hydrodeoxygenation of Bio-Oil Model Compounds over Pt/HBEA
Foo, G. S., Rogers, A. K., Yung, M. M., & Sievers, C. (2016) · ACS Catalysis · doi:10.1021/acscatal.5b02684 · Cited by 139 · see citing works
Impact of acid site speciation and spatial gradients on zeolite catalysis
Le, T. T., Chawla, A., & Rimer, J. D. (2020) · Journal of Catalysis · doi:10.1016/j.jcat.2020.08.008 · Cited by 125 · see citing works
Water structures on acidic zeolites and their roles in catalysis
Liu, Q., & van Bokhoven, J. A. (2024) · Chemical Society Reviews · doi:10.1039/d3cs00404j · Cited by 118 · see citing works
Cooperativity between Al Sites Promotes Hydrogen Transfer and Carbon–Carbon Bond Formation upon Dimethyl Ether Activation on Alumina
Comas‐Vives, A., Valla, M., Copéret, C., & Sautet, P. (2015) · ACS Central Science · doi:10.1021/acscentsci.5b00226 · Cited by 115 · see citing works
Computational Assessment of the Dominant Factors Governing the Mechanism of Methanol Dehydration over H-ZSM-5 with Heterogeneous Aluminum Distribution
Ghorbanpour, A., Rimer, J. D., & Grabow, L. C. (2016) · ACS Catalysis · doi:10.1021/acscatal.5b02367 · Cited by 113 · see citing works
Deactivation of Zeolites and Zeotypes in Methanol-to-Hydrocarbons Catalysis: Mechanisms and Circumvention
Hwang, A., & Bhan, A. (2019) · Accounts of Chemical Research · doi:10.1021/acs.accounts.9b00204 · Cited by 112 · see citing works
Direct Synthesis of Dimethyl Ether from CO2: Recent Advances in Bifunctional/Hybrid Catalytic Systems
Mota, N., Ordóñez, E. M., Pawelec, B., Fierro, J. L. G., & Navarro, R. M. (2021) · Catalysts · doi:10.3390/catal11040411 · Cited by 107 · see citing works
Similarities and differences between aromatic-based and olefin-based cycles in H-SAPO-34 and H-SSZ-13 for methanol-to-olefins conversion: insights from energetic span model
Wang, C., Wang, Y., Du, Y., Yang, G., & Xie, Z. (2015) · Catalysis Science & Technology · doi:10.1039/c5cy00483g · Cited by 104 · see citing works
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An, H., Zhang, F., Guan, Z., Liu, X., Fan, F., & Li, C. (2018) · ACS Catalysis · doi:10.1021/acscatal.8b00928 · Cited by 102 · see citing works
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Simons, M. C., Prinslow, S. D., Babucci, M., Hoffman, A. S., Hong, J., Vitillo, J. G., Bare, S. R., Gates, B. C., Lu, C. C., Gagliardi, L., et al. (2021) · Journal of the American Chemical Society · doi:10.1021/jacs.1c04766 · Cited by 102 · see citing works
Carbocation chemistry confined in zeolites: spectroscopic and theoretical characterizations
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Foo, G. S., Polo‐Garzon, F., Fung, V., Jiang, D., Overbury, S. H., & Wu, Z. (2017) · ACS Catalysis · doi:10.1021/acscatal.7b00783 · Cited by 95 · see citing works
Zeolite-catalysed C–C bond forming reactions for biomass conversion to fuels and chemicals
Resasco, D. E., Wang, B., & Crossley, S. P. (2016) · Catalysis Science & Technology · doi:10.1039/c5cy02271a · Cited by 94 · see citing works
Reaction path analysis for 1-butanol dehydration in H-ZSM-5 zeolite: Ab initio and microkinetic modeling
John, M., Alexopoulos, K., Reyniers, M., & Marin, G. B. (2015) · Journal of Catalysis · doi:10.1016/j.jcat.2015.07.005 · Cited by 92 · see citing works
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Bahruji, H., Armstrong, R. D., Esquius, J. R., Jones, W., Bowker, M., & Hutchings, G. J. (2018) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.8b00230 · Cited by 82 · see citing works
Benzene co-reaction with methanol and dimethyl ether over zeolite and zeotype catalysts: Evidence of parallel reaction paths to toluene and diphenylmethane
Martinez‐Espin, J. S., Wispelaere, K. D., Erichsen, M. W., Svelle, S., Janssens, T. V. W., Speybroeck, V. V., Beato, P., & Olsbye, U. (2017) · Journal of Catalysis · doi:10.1016/j.jcat.2017.03.007 · Cited by 82 · see citing works
Operando Modeling of Zeolite-Catalyzed Reactions Using First-Principles Molecular Dynamics Simulations
Speybroeck, V. V., Bocus, M., Cnudde, P., & Vanduyfhuys, L. (2023) · ACS Catalysis · doi:10.1021/acscatal.3c01945 · Cited by 80 · see citing works
Eley–Rideal, the Other Mechanism
Prins, R. (2018) · Topics in Catalysis · doi:10.1007/s11244-018-0948-8 · Cited by 80 · see citing works
Pathways of Methane Transformation over Copper‐Exchanged Mordenite as Revealed by In Situ NMR and IR Spectroscopy
Sushkevich, V. L., Verel, R., & van Bokhoven, J. A. (2019) · Angewandte Chemie International Edition · doi:10.1002/anie.201912668 · Cited by 77 · see citing works
Review and perspective: Next generation DME synthesis technologies for the energy transition
Peinado, C., Liuzzi, D., Sluijter, S. N., Skorikova, G. S., Boon, J., Guffanti, S., Groppi, G., & Rojas, S. (2023) · Chemical Engineering Journal · doi:10.1016/j.cej.2023.147494 · Cited by 74 · see citing works
Development of Heterogeneous Catalysts for Dehydration of Methanol to Dimethyl Ether: A Review
Bateni, H., & Able, C. M. (2019) · Catalysis in Industry · doi:10.1134/s2070050419010045 · Cited by 69 · see citing works
The Oxygenate-Mediated Conversion of CO x to Hydrocarbons─On the Role of Zeolites in Tandem Catalysis
Xie, J., & Olsbye, U. (2023) · Chemical Reviews · doi:10.1021/acs.chemrev.3c00058 · Cited by 69 · see citing works
Mechanistic insights into aqueous phase propanol dehydration in H‐ZSM‐5 zeolite
Mei, D., & Lercher, J. A. (2016) · AIChE Journal · doi:10.1002/aic.15517 · Cited by 68 · see citing works
Room temperature methoxylation in zeolites: insight into a key step of the methanol-to-hydrocarbons process
O’Malley, A. J., Parker, S. F., Chutia, A., Farrow, M. R., Silverwood, I. P., Sakai, V. G., & Catlow, C. R. A. (2015) · Chemical Communications · doi:10.1039/c5cc08956e · Cited by 67 · see citing works
Ferrierite vs. γ-Al2O3: The superiority of zeolites in terms of water-resistance in vapour-phase dehydration of methanol to dimethyl ether
Catizzone, E., Migliori, M., Purita, A., & Giordano, G. (2018) · Journal of Energy Chemistry · doi:10.1016/j.jechem.2018.05.004 · Cited by 64 · see citing works
Mechanistic origins of the high-pressure inhibition of methanol dehydration rates in small-pore acidic zeolites
Di Iorio, J. R., Hoffman, A. J., Nimlos, C. T., Nystrom, S., Hibbitts, D., & Gounder, R. (2019) · Journal of Catalysis · doi:10.1016/j.jcat.2019.10.012 · Cited by 61 · see citing works
Mechanism and Kinetics of Methylating C 6 –C 12 Methylbenzenes with Methanol and Dimethyl Ether in H-MFI Zeolites
DeLuca, M., Kravchenko, P., Hoffman, A. J., & Hibbitts, D. D. (2019) · ACS Catalysis · doi:10.1021/acscatal.9b00650 · Cited by 61 · see citing works
Reactivity descriptors in acid catalysis: acid strength, proton affinity and host–guest interactions
Deshlahra, P., & Enrique Iglesia, A. (2020) · Chemical Communications · doi:10.1039/d0cc02593c · Cited by 59 · see citing works
Complex Reaction Environments and Competing Reaction Mechanisms in Zeolite Catalysis: Insights from Advanced Molecular Dynamics
Wispelaere, K. D., Ensing, B., Ghysels, A., Meijer, E. J., & Speybroeck, V. V. (2015) · Chemistry - A European Journal · doi:10.1002/chem.201500473 · Cited by 59 · see citing works
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Allen, M. C., Hoffman, A. J., Liu, T.-W., Webber, M. S., Hibbitts, D. D., & Schwartz, T. J. (2020) · ACS Catalysis · doi:10.1021/acscatal.0c01328 · Cited by 55 · see citing works
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Li, S., Guo, L., He, X., Qiao, C., & Tian, Y. (2022) · Renewable Energy · doi:10.1016/j.renene.2022.05.052 · Cited by 56 · see citing works
Effects of Local Water Concentrations on Cyclohexanol Dehydration in H-BEA Zeolites
Mei, D., & Lercher, J. A. (2019) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.9b07738 · Cited by 56 · see citing works
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Nastase, S. A. F., Cnudde, P., Vanduyfhuys, L., Wispelaere, K. D., Speybroeck, V. V., Catlow, C. R. A., & Logsdail, A. J. (2020) · ACS Catalysis · doi:10.1021/acscatal.0c01454 · Cited by 56 · see citing works
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Wang, C., Wang, Y., & Xie, Z. (2016) · Catalysis Science & Technology · doi:10.1039/c6cy01095d · Cited by 55 · see citing works
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Erichsen, M. W., Wispelaere, K. D., Hemelsoet, K., Moors, S. L. C., Deconinck, T., Waroquier, M., Svelle, S., Speybroeck, V. V., & Olsbye, U. (2015) · Journal of Catalysis · doi:10.1016/j.jcat.2015.01.013 · Cited by 54 · see citing works
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Pleßow, P. N., & Studt, F. (2018) · Catalysis Letters · doi:10.1007/s10562-018-2330-7 · Cited by 53 · see citing works
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Nystrom, S. V., Hoffman, A. J., & Hibbitts, D. D. (2018) · ACS Catalysis · doi:10.1021/acscatal.8b02049 · Cited by 52 · see citing works
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Lyu, Y., Xu, R., Williams, O. C., Wang, Z., & Sievers, C. (2021) · Journal of Catalysis · doi:10.1016/j.jcat.2021.10.004 · Cited by 50 · see citing works
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Foo, G. S., Hu, G., Hood, Z. D., Li, M., Jiang, D., & Wu, Z. (2017) · ACS Catalysis · doi:10.1021/acscatal.7b01456 · Cited by 50 · see citing works
Kinetic Modeling of Catalytic Olefin Cracking and Methanol-to-Olefins (MTO) over Zeolites: A Review
Standl, S., & Hinrichsen, O. (2018) · Catalysts · doi:10.3390/catal8120626 · Cited by 49 · see citing works
First-principles kinetic study on benzene alkylation with ethanol vs. ethylene in H-ZSM-5
Wang, D., Wang, C., Yang, G. H., Du, Y., & Yang, W. (2019) · Journal of Catalysis · doi:10.1016/j.jcat.2019.04.021 · Cited by 49 · see citing works
Shape selective catalysis in methylation of toluene: Development, challenges and perspectives
Zhou, J., Liu, Z., Wang, Y., Kong, D., & Xie, Z. (2017) · Frontiers of Chemical Science and Engineering · doi:10.1007/s11705-017-1671-x · Cited by 48 · see citing works
How Accurately Do Approximate Density Functionals Predict Trends in Acidic Zeolite Catalysis?
Pleßow, P. N., & Studt, F. (2020) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.0c01240 · Cited by 47 · see citing works
Towards molecular control of elementary reactions in zeolite catalysis by advanced molecular simulations mimicking operating conditions
Wispelaere, K. D., Bailleul, S., & Speybroeck, V. V. (2016) · Catalysis Science & Technology · doi:10.1039/c5cy02073e · Cited by 45 · see citing works
Influence of Tetrapropylammonium and Ethylenediamine Structure-Directing Agents on the Framework Al Distribution in B–Al–MFI Zeolites
Hur, Y. G., Kester, P. M., Nimlos, C. T., Cho, Y., Miller, J. T., & Gounder, R. (2019) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.9b01726 · Cited by 44 · see citing works
Rigid Arrangements of Ionic Charge in Zeolite Frameworks Conferred by Specific Aluminum Distributions Preferentially Stabilize Alkanol Dehydration Transition States
Hoffman, A. J., Bates, J. S., Iorio, J. R. D., Nystrom, S. V., Nimlos, C. T., Gounder, R., & Hibbitts, D. D. (2020) · Angewandte Chemie International Edition · doi:10.1002/anie.202007790 · Cited by 44 · see citing works
Pathways of Methane Transformation over Copper‐Exchanged Mordenite as Revealed by In Situ NMR and IR Spectroscopy
Sushkevich, V. L., Verel, R., & van Bokhoven, J. A. (2019) · Angewandte Chemie · doi:10.1002/ange.201912668 · Cited by 42 · see citing works
Recent Progress in Direct DME Synthesis and Potential of Bifunctional Catalysts
Banivaheb, S., Pitter, S., Delgado, K. H., Rubín, M., Sauer, J., & Dittmeyer, R. (2022) · Chemie Ingenieur Technik · doi:10.1002/cite.202100167 · Cited by 41 · see citing works
Reactivity of Surface Lewis and Brønsted Acid Sites in Zeolite Catalysis: A Computational Case Study of DME Synthesis Using H-SSZ-13
Huber, P., Studt, F., & Plessow, P. N. (2022) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.2c00668 · Cited by 39 · see citing works
Single-event kinetic model for methanol-to-olefins (MTO) over ZSM-5: Fundamental kinetics for the olefin co-feed reactivity
Standl, S., Kirchberger, F. M., Kuehlewind, T., Tonigold, M., Sanchez‐Sanchez, M., Lercher, J. A., & Hinrichsen, O. (2020) · Chemical Engineering Journal · doi:10.1016/j.cej.2020.126023 · Cited by 38 · see citing works
Mechanistic differences between methanol and dimethyl ether in zeolite-catalyzed hydrocarbon synthesis
Kirchberger, F. M., Liu, Y., Pleßow, P. N., Tonigold, M., Studt, F., Sanchez‐Sanchez, M., & Lercher, J. A. (2022) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.2103840119 · Cited by 35 · see citing works
Catalytic Dehydration of Biomass Derived 1-Propanol to Propene over M-ZSM-5 (M = H, V, Cu, or Zn)
Lepore, A. W., Li, Z., Davison, B. H., Foo, G. S., Wu, Z., & Narula, C. K. (2017) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.7b00592 · Cited by 34 · see citing works
Molecular behaviour of methanol and dimethyl ether in H-ZSM-5 catalysts as a function of Si/Al ratio: a quasielastic neutron scattering study
Omojola, T., Silverwood, I. P., & O’Malley, A. J. (2020) · Catalysis Science & Technology · doi:10.1039/d0cy00670j · Cited by 34 · see citing works
Restructuring of MFI Framework Zeolite Models and Their Associated Artifacts in Density Functional Theory Calculations
Hoffman, A. J., DeLuca, M., & Hibbitts, D. D. (2019) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.8b12230 · Cited by 33 · see citing works
Mechanisms and Kinetics of the Dehydrogenation of C6–C8 Cycloalkanes, Cycloalkenes, and Cyclodienes to Aromatics in H-MFI Zeolite Framework
Montalvo-Castro, H., DeLuca, M., Kilburn, L., & Hibbitts, D. D. (2022) · ACS Catalysis · doi:10.1021/acscatal.2c03360 · Cited by 32 · see citing works
Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments
Wispelaere, K. D., Martinez‐Espin, J. S., Hoffmann, M. J., Svelle, S., Olsbye, U., & Bligaard, T. (2018) · Catalysis Today · doi:10.1016/j.cattod.2018.02.042 · Cited by 32 · see citing works
A Systematic Study of Methylation from Benzene to Hexamethylbenzene in H-SSZ-13 Using Density Functional Theory and Ab Initio Calculations
Fečík, M., Pleßow, P. N., & Studt, F. (2020) · ACS Catalysis · doi:10.1021/acscatal.0c02037 · Cited by 30 · see citing works
Mechanism and kinetics of 1-dodecanol etherification over tungstated zirconia
Rorrer, J. E., He, Y., Toste, F. D., & Bell, A. T. (2017) · Journal of Catalysis · doi:10.1016/j.jcat.2017.08.001 · Cited by 29 · see citing works
A temporal analysis of products (TAP) study of C2-C4 alkene reactions with a well-defined pool of methylating species on ZSM-22 zeolite
Redekop, E., Lazzarini, A., Bordiga, S., & Olsbye, U. (2020) · Journal of Catalysis · doi:10.1016/j.jcat.2020.03.020 · Cited by 29 · see citing works
Comparing alkene-mediated and formaldehyde-mediated diene formation routes in methanol-to-olefins catalysis in MFI and CHA
Kilburn, L., DeLuca, M., Hoffman, A. J., Patel, S., & Hibbitts, D. D. (2021) · Journal of Catalysis · doi:10.1016/j.jcat.2021.05.010 · Cited by 29 · see citing works
Ethanol dehydration on γ-Al2O3: Effects of partial pressure and temperature
Lee, J., Szanyi, J., & Kwak, J. H. (2017) · Molecular Catalysis · doi:10.1016/j.mcat.2016.12.013 · Cited by 28 · see citing works
Direct DME synthesis on CZZ/H-FER from variable CO 2 /CO syngas feeds
Wild, S., Polierer, S., Zevaco, T. A., Guse, D., Kind, M., Pitter, S., Delgado, K. H., & Sauer, J. (2021) · RSC Advances · doi:10.1039/d0ra09754c · Cited by 28 · see citing works
CO 2 to dimethyl ether (DME): structural and functional insights of hybrid catalysts
Ghosh, A., Nag, D., Chatterjee, R., Singha, A., Dash, P. S., Chowdhury, B., & Bhaumik, A. (2024) · Catalysis Science & Technology · doi:10.1039/d3cy01497e · Cited by 26 · see citing works
Ammonia Titration Methods To Quantify Brønsted Acid Sites in Zeolites Substituted with Aluminum and Boron Heteroatoms
Kester, P. M., Miller, J. T., & Gounder, R. (2018) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.8b00933 · Cited by 27 · see citing works
Influence of Acidity on the Methanol-to-DME Reaction in Zeotypes: A First Principles-Based Microkinetic Study
Arvidsson, A. A., Plessow, P. N., Studt, F., & Hellman, A. (2020) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.0c03125 · Cited by 27 · see citing works
Cooperative catalytically active sites for methanol activation by single metal ion-doped H-ZSM-5
Lin, W.-C., Wu, S., Li, G., Ho, P.-L., Ye, Y., Zhao, P., Day, S. J., Tang, C. C., Chen, W., Zheng, A., et al. (2020) · Chemical Science · doi:10.1039/d0sc04058d · Cited by 26 · see citing works
Trends and Outlook of Computational Chemistry and Microkinetic Modeling for Catalytic Synthesis of Methanol and DME
Park, J., Kim, H. S., Lee, W. B., & Park, M. (2020) · Catalysts · doi:10.3390/catal10060655 · Cited by 25 · see citing works
Insight into the Methylation of Alkenes and Aromatics with Methanol over Zeolite Catalysts by Linear Scaling Relations
Chen, Y., Zhao, X., Qin, Z., Wang, S., Wei, Z., Li, J., Dong, M., Wang, J., & Fan, W. (2020) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.0c03405 · Cited by 23 · see citing works
Microkinetic modeling of DME synthesis from methanol over H-zeolite catalyst: Associative vs. dissociative pathways
Park, J., Cho, J., Park, M., & Lee, W. B. (2020) · Catalysis Today · doi:10.1016/j.cattod.2020.02.011 · Cited by 22 · see citing works
Cooperative Adsorption: Solvating the Hofmann Elimination of Alkylamines
Chen, H., & Abdelrahman, O. A. (2021) · ACS Catalysis · doi:10.1021/acscatal.1c01364 · Cited by 22 · see citing works
Effect of Aluminum Siting in H-ZSM-5 on Reaction Barriers
Smith, A. T., Pleßow, P. N., & Studt, F. (2021) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.1c06670 · Cited by 21 · see citing works
Quantifying Effects of Active Site Proximity on Rates of Methanol Dehydration to Dimethyl Ether over Chabazite Zeolites through Microkinetic Modeling
Marsden, G., Kostetskyy, P., Sekiya, R.-S., Hoffman, A. J., Lee, S., Gounder, R., Hibbitts, D. D., & Broadbelt, L. J. (2021) · ACS Materials Au · doi:10.1021/acsmaterialsau.1c00057 · Cited by 21 · see citing works
Insight into the Role of Water on the Methylation of Hexamethylbenzene in H‐SAPO‐34 from First Principle Molecular Dynamics Simulations
Bailleul, S., Rogge, S. M. J., Vanduyfhuys, L., & Speybroeck, V. V. (2019) · ChemCatChem · doi:10.1002/cctc.201900618 · Cited by 20 · see citing works
Rigid Arrangements of Ionic Charge in Zeolite Frameworks Conferred by Specific Aluminum Distributions Preferentially Stabilize Alkanol Dehydration Transition States
Hoffman, A. J., Bates, J. S., Iorio, J. R. D., Nystrom, S. V., Nimlos, C. T., Gounder, R., & Hibbitts, D. D. (2020) · Angewandte Chemie · doi:10.1002/ange.202007790 · Cited by 21 · see citing works
Clustering of alkanols confined in chabazite zeolites: Kinetic implications for dehydration of methanol-ethanol mixtures
Bates, J. S., & Gounder, R. (2020) · Journal of Catalysis · doi:10.1016/j.jcat.2020.07.027 · Cited by 20 · see citing works
Acid Sites of Phosphorus-Modified Zeosils
Kumar, G., Ren, L., Pang, Y., Li, X., Chen, H., Gulbinski, J., Dauenhauer, P. J., Michael Tsapatsis, B., & Abdelrahman, O. A. (2021) · ACS Catalysis · doi:10.1021/acscatal.1c01588 · Cited by 20 · see citing works
On the Redox Mechanism of Low‐Temperature NH3‐SCR over Cu‐CHA: A Combined Experimental and Theoretical Study of the Reduction Half Cycle
Hu, W., Selleri, T., Gramigni, F., Fenes, E., Rout, K. R., Liu, S., Nova, I., Chen, D., Gao, X., & Tronconi, E. (2021) · Angewandte Chemie · doi:10.1002/ange.202014926 · Cited by 19 · see citing works
On the conversion of CO 2 to value added products over composite PdZn and H-ZSM-5 catalysts: excess Zn over Pd, a compromise or a penalty?
Ahoba-Sam, C., Borfecchia, E., Lazzarini, A., Bugaev, A. L., Isah, A. A., Taoufik, M., Bordiga, S., & Olsbye, U. (2020) · Catalysis Science & Technology · doi:10.1039/d0cy00440e · Cited by 18 · see citing works
Simple Scheme to Predict Transition-State Energies of Dehydration Reactions in Zeolites with Relevance to Biomass Conversion
Fečík, M., Pleßow, P. N., & Studt, F. (2018) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.8b07659 · Cited by 17 · see citing works
Chloromethane to olefins over H-SAPO-34: Probing the hydrocarbon pool mechanism
Fickel, D. W., Sabnis, K. D., Li, L., Kulkarni, N., Winter, L. R., Yan, B., & Chen, J. G. (2016) · Applied Catalysis A General · doi:10.1016/j.apcata.2016.09.004 · Cited by 16 · see citing works
Elucidation of the mechanism and structure–reactivity relationship in zeolite catalyzed alkylation of benzene with propylene
Xing, S., Liu, K., Wang, T., Zhang, R., & Han, M. (2021) · Catalysis Science & Technology · doi:10.1039/d0cy02374d · Cited by 16 · see citing works
Dehydration of 1-Octadecanol over H-BEA: A Combined Experimental and Computational Study
Song, W., Liu, Y., Baráth, E., Wang, L. L., Zhao, C., Mei, D., & Lercher, J. A. (2015) · ACS Catalysis · doi:10.1021/acscatal.5b01217 · Cited by 16 · see citing works
A kinetic study on the methanol conversion to dimethyl ether over H-ZSM-5 zeolite
Trypolskyi, A., Zhokh, A. A., Gritsenko, V. I., Chen, M., Tang, J., & Strizhak, P. E. (2021) · Chemical Papers · doi:10.1007/s11696-021-01586-y · Cited by 15 · see citing works
Acidity effect on benzene methylation kinetics over substituted H-MeAlPO-5 catalysts
Mortén, M., Cordero‐Lanzac, T., Cnudde, P., Redekop, E., Svelle, S., Speybroeck, V. V., & Olsbye, U. (2021) · Journal of Catalysis · doi:10.1016/j.jcat.2021.11.002 · Cited by 15 · see citing works
Solvent tunes the selectivity of alkenes epoxidation over Ti-Beta Zeolite: A systematic kinetic assessment on elementary steps, kinetically relevant and reaction barriers
He, Z., Lei, Q., Dai, W., & Zhang, H. (2023) · Journal of Catalysis · doi:10.1016/j.jcat.2023.03.012 · Cited by 15 · see citing works
Recent Advances for Selective Catalysis in Benzene Methylation: Reactions, Shape-Selectivity and Perspectives
Wang, D., Su, X., Fan, Z., Wen, Z., Li, N., & Yang, Y. (2021) · Catalysis Surveys from Asia · doi:10.1007/s10563-021-09337-5 · Cited by 15 · see citing works
Confinement and surface sites control methanol adsorbate stability on MFI zeolites, SBA-15, and a silica-supported heteropoly acid
Li, Z., Dittmann, D., Rieg, C., Benz, M., & Dyballa, M. (2022) · Catalysis Science & Technology · doi:10.1039/d1cy02330f · Cited by 14 · see citing works
Monitoring the methanol conversion process in H-ZSM-5 using synchrotron X-ray powder diffraction-mass spectrometry
Lo, T. W. B., Ye, L., Murray, C. A., Tang, C. C., Mei, D., & Tsang, S. C. E. (2018) · Journal of Catalysis · doi:10.1016/j.jcat.2018.06.027 · Cited by 14 · see citing works

Theoretical Study of the Mechanism of Surface Methoxy and Dimethyl Ether Formation from Methanol Catalyzed by Zeolitic Protons
Blaszkowski, S. R., & van Santen, R. A. (1997) · The Journal of Physical Chemistry B · doi:10.1021/jp962006+ · Cited by 181 · see citing works
Computational Assessment of the Dominant Factors Governing the Mechanism of Methanol Dehydration over H-ZSM-5 with Heterogeneous Aluminum Distribution
Ghorbanpour, A., Rimer, J. D., & Grabow, L. C. (2016) · ACS Catalysis · doi:10.1021/acscatal.5b02367 · Cited by 113 · see citing works
Microkinetic modeling of DME synthesis from methanol over H-zeolite catalyst: Associative vs. dissociative pathways
Park, J., Cho, J., Park, M., & Lee, W. B. (2020) · Catalysis Today · doi:10.1016/j.cattod.2020.02.011 · Cited by 22 · see citing works
Methanol adsorption and activation by zeolitic protons
Blaszkowski, S. R., & van Santen, R. A. (1997) · TU/e Research Portal
Kinetics of the dehydration of methanol to methyl ether on an ultrahigh-silica zeolite
Sinitsyna, O. A., Chumakova, V. N., & Moskovskaya, I. F. (1987) · OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information)

Authors: Jones, A. J., & Iglesia, E.
Affiliations: University of California, Berkeley (US)
ORCID: Jones, Andrew J.
Venue: Angewandte Chemie International Edition
Publisher: Wiley
Published: 2014-09-11
Volume: 53
Issue: 45
Pages: 12177-12181
ISSN: 1433-7851 (ISSN-L)
1521-3773
DOI: 10.1002/anie.201406823
OpenAlex: W2121218313
Cited by: 142
References: 28
Citations by year: 2026: 6 · 2025: 5 · 2024: 8 · 2023: 11 · 2022: 12 · 2021: 22 · 2020: 18 · 2019: 17 · 2018: 14 · 2017: 12 · 2016: 7 · 2015: 10
FWCI: 4.11
Type: journal article
Language: en
Open access: closed
Licence: onlinelibrary.wiley.com/termsAndConditions#vor (vor)
Locations: Angewandte Chemie International Edition (publishedVersion)
PubMed (publishedVersion)
Topics: Physical Sciences › Chemistry › Inorganic Chemistry › Zeolite Catalysis and Synthesis
Physical Sciences › Chemical Engineering › Catalysis › Catalysis and Oxidation Reactions
Physical Sciences › Chemistry › Organic Chemistry › Chemical Synthesis and Reactions
Keywords: methanol dehydration, zeolites, dimethyl ether, methoxy intermediate, reaction mechanism, transition state, activation free energy, in situ infrared spectroscopy, density functional theory, van der Waals interactions, hydrocarbon synthesis

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Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites

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