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Insight into the effects of confined hydrocarbon species on the lifetime of methanol conversion catalysts


The methanol-to-hydrocarbons reaction refers collectively to a series of important industrial catalytic processes to produce either olefins or gasoline. Mechanistically, methanol conversion proceeds through a ‘pool’ of hydrocarbon species. For the methanol-to-olefins process, these species can be delineated broadly into ‘desired’ lighter olefins and ‘undesired’ heavier fractions that cause deactivation in a matter of hours. The crux in further catalyst optimization is the ability to follow the formation of carbonaceous species during operation. Here, we report the combined results of an operando Kerr-gated Raman spectroscopic study with state-of-the-art operando molecular simulations, which allowed us to follow the formation of hydrocarbon species at various stages of methanol conversion. Polyenes are identified as crucial intermediates towards formation of polycyclic aromatic hydrocarbons, with their fate determined largely by the zeolite topology. Notably, we provide the missing link between active and deactivating species, which allows us to propose potential design rules for future-generation catalysts.

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Fig. 1: Different stages of the MTO reaction and the Kerr-gate Raman spectroscopy set-up.
Fig. 2: Operando Kerr-gated Raman spectroscopy of SSZ-13 zeolite during the MTO reaction; formation of hydrocarbon pool intermediates and onset of deactivation.
Fig. 3: Comparison of experimental and simulated Raman spectra.
Fig. 4: Mobility of polyene species that are formed at the onset of deactivation.
Fig. 5: Operando Kerr-gated Raman spectroscopy of SSZ-13 zeolite during the MTO reaction; formation of PAHs and comparison with ZSM-5 and SAPO-34 archetypal MTH catalysts.
Fig. 6: Hydrocarbon species evolution during the MTO reaction on small-pore catalyst materials.

Data availability

Source data are provided with this paper. Example CP2K input files and processing scripts are available from the public GitHub online repository at Owing to the large size of the molecular dynamics trajectories and CP2K output files, they are available upon author request instead.


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This research has been performed with the use of facilities including a Raman spectrometer and thermogravimetric analysis equipment at the Research Complex at Harwell. We thank the Research Complex for access and support to these facilities and equipment. We acknowledge the Engineering and Physical Sciences Research Council for funding grants EP/K007467/1, EP/K014706/2, EP/K014668/1, EP/K014854/1, EP/K014714/1, EP/M013219/1, EP/S016481/1 and EP/S016481/1. The Science and Technology Facilities Council (STFC) is acknowledged for the beam time at the ULTRA facility for performing Kerr-gate experiments. L. Mantarosie (Johnson Matthey PLC) is also thanked for her assistance and expertise. P. Matousek and T. Parker (STFC) are acknowledged for useful discussions. V.V.S., A.E.J.H. and M.B. acknowledge the Research Foundation – Flanders (FWO), the Special Research Fund of Ghent University, and funding from the Horizon 2020 research and innovation program of the European Union (consolidator European Research Council grant agreement no. 647755 – DYNPOR (2015–2020)). The computational resources and services were provided by Ghent University (Stevin Supercomputer Infrastructure) and the Flemish Supercomputer Center, and funded by the FWO.

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Authors and Affiliations



I.L.-G. and A.M.B. conceived and coordinated the project with V.V.S., M.T. and I.V.S. as close collaborators. I.L.-G. performed the operando Kerr-gated Raman experiments, and E.C., M.A.-A., E.K.G., A.G. and I.V.S. supported the work. A.E.J.H., M.B., K.d.W. and V.V.S. performed the molecular simulations. I.L.-G., E.C., A.E.J.H., V.V.S., K.d.W., A.M.B., M.T. and I.V.S. contributed to the data analysis and discussion. I.L.-G., E.C., A.E.J.H., V.V.S. and A.M.B. wrote the manuscript with input from all authors.

Corresponding authors

Correspondence to I. Lezcano-Gonzalez, V. Van Speybroeck or A. M. Beale.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–43, Tables 1–2 and Refs. 1–44.

Source data

Source Data Fig. 2

Processed Kerr-gated Raman data recorded during the MTH reaction between 250 and 300 °C on SSZ-13 zeolite; processed mass spectrometry data recorded during the MTH reaction between 240 and 310 °C on SSZ-13 zeolite.

Source Data Fig. 3

Comparison between processed Kerr-gated Raman data recorded during the MTH reaction at 260, 280 and 300 °C and the simulated spectra of propene, isoprene, butadiene, trimethylnaphthalene, trimethylbenzene, dimethylpentadiene and heptatriene.

Source Data Fig. 4

Position of the centre of mass of the carbon atoms projected on one of the 8-ring channels and a direction perpendicular to it for the intermediates propene, heptatriene and decapentaene.

Source Data Fig. 5

Processed Kerr-gated Raman data recorded during the MTH reaction between 320 and 450 °C on SSZ-13 zeolite; simulated Raman spectra of anthracene and anthracene precursor; processed Kerr-gated Raman data recorded after quenching the MTH reaction at 450 °C in SSZ-13, ZSM-5 and SAPO-34 catalyst materials.

Source Data Fig. S3

Processed Kerr-gated Raman data recorded before and after methanol adsorption at 100 °C on SSZ-13 zeolite.

Source Data Fig. S4

Processed Kerr-gated Raman data recorded during the MTH reaction between 100 and 240 °C on SSZ-13 zeolite; processed mass spectrometry data recorded during the MTH reaction between 100 and 250 °C on SSZ-13 zeolite.

Source Data Fig. S38

Processed Kerr-gated Raman data recorded during the MTH reaction on SSZ-13 zeolite under isothermal conditions at 280 and 350 °C; processed mass spectrometry data recorded during the MTH reaction on SSZ-13 zeolite under isothermal conditions at 280 and 350 °C.

Source Data Fig. S39

Processed Kerr-gated Raman data recorded during the MTH reaction between 280 and 340 °C on ZSM-5 zeolite; processed mass spectrometry data recorded during the MTH reaction between 260 and 350 °C on ZSM-5 zeolite; processed Kerr-gated Raman data recorded during the MTH reaction between 360 and 450 °C on ZSM-5 zeolite.

Source Data Fig. S40

Processed Kerr-gated Raman data recorded during the MTH reaction between 210 and 450 °C on SAPO-34; processed mass spectrometry data recorded during the MTH reaction between 250 and 350 °C on SAPO-34.

Source Data Fig. S41

Processed Raman data recorded using a lab-based Raman spectrometer (830 nm) for SSZ-13 zeolite after the MTH reaction at 450 °C and for Mo/H-ZSM-5 zeolite after methane dehydroaromatization at 700 °C for 30 h (GHSV 1500 h−1).

Source Data Fig. S42

Thermogravimetric analysis of SSZ-13 zeolite after the MTH reaction at 450 °C.

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Lezcano-Gonzalez, I., Campbell, E., Hoffman, A.E.J. et al. Insight into the effects of confined hydrocarbon species on the lifetime of methanol conversion catalysts. Nat. Mater. 19, 1081–1087 (2020).

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