Nano-scale insights regarding coke formation in zeolite SSZ-13 subject to the methanol-to-hydrocarbons reaction

S. H. van Vreeswijk; M. Monai; R. Oord; J. E. Schmidt; E. T. C. Vogt; J. D. Poplawsky; B. M. Weckhuysen

doi:10.1039/d1cy01938d

Nano-scale insights regarding coke formation in zeolite SSZ-13 subject to the methanol-to-hydrocarbons reaction

S. H. van Vreeswijk, M. Monai, R. Oord, J. E. Schmidt, E. T. C. Vogt^*, J. D. Poplawsky^*, B. M. Weckhuysen^*

^*Corresponding author for this work

Oak Ridge National Laboratory

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

The methanol-to-hydrocarbons (MTH) process, commonly catalyzed by zeolites, is of great commercial interest and therefore widely studied both in industry and academia. However, zeolite-based catalyst materials are notoriously hard to study at the nano-scale. Atom probe tomography (APT) is uniquely positioned among the suite of characterization techniques, as it can provide 3D chemical information with sub-nm resolution. In this work, we have used APT to study the nano-scale coking behavior of zeolite SSZ-13 and its relation to bulk coke formation on the macro-/micro-scale studied with operando and in situ UV-vis spectroscopy and microscopy. Radial distribution function analysis (RDF) of the APT data revealed short carbon–carbon length scale affinities, consistent with the formation of larger aromatic molecules (coke species). Using nearest neighbor distribution (NND) analysis, an increase in the homogeneity of carbon was found with increasing time-on-stream. However, carbon clusters could not be isolated due to spatial noise and limited clustering. Therefore, it was found that the coke formation in zeolite SSZ-13 (CHA) is reasonably homogeneous on the nano-scale, and is rather similar to the silicoaluminophosphate analogue SAPO-34 (CHA) but different in nano-scale coking behavior compared to previously studied zeolite ZSM-5 (MFI).

Original language	English
Pages (from-to)	1220-1228
Number of pages	9
Journal	Catalysis Science & Technology
Volume	12
Issue number	4
Early online date	8 Jan 2022
DOIs	https://doi.org/10.1039/d1cy01938d
Publication status	Published - 21 Feb 2022

Bibliographical note

Funding Information:
This work is supported by the ARC-CBBC (Advanced Research Center – Chemical Building Blocks Consortium), which is cofounded and co-financed by the Netherlands Organisation for Scientific Research (NWO) and the Netherlands Ministry of Economic Affairs and Climate Policy, in collaboration with BASF. APT was conducted at ORNL's Center for Nanophase Materials Sciences (CNMS), which is a U.S. DOE Office of Science User Facility. The authors would like to thank James Burns (ORNL) for assistance in performing APT sample preparation and running the APT experiments.

Publisher Copyright:
© The Royal Society of Chemistry.

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@article{aa9024b8c6834bd69e39554f5d2895f7,

title = "Nano-scale insights regarding coke formation in zeolite SSZ-13 subject to the methanol-to-hydrocarbons reaction",

abstract = "The methanol-to-hydrocarbons (MTH) process, commonly catalyzed by zeolites, is of great commercial interest and therefore widely studied both in industry and academia. However, zeolite-based catalyst materials are notoriously hard to study at the nano-scale. Atom probe tomography (APT) is uniquely positioned among the suite of characterization techniques, as it can provide 3D chemical information with sub-nm resolution. In this work, we have used APT to study the nano-scale coking behavior of zeolite SSZ-13 and its relation to bulk coke formation on the macro-/micro-scale studied with operando and in situ UV-vis spectroscopy and microscopy. Radial distribution function analysis (RDF) of the APT data revealed short carbon–carbon length scale affinities, consistent with the formation of larger aromatic molecules (coke species). Using nearest neighbor distribution (NND) analysis, an increase in the homogeneity of carbon was found with increasing time-on-stream. However, carbon clusters could not be isolated due to spatial noise and limited clustering. Therefore, it was found that the coke formation in zeolite SSZ-13 (CHA) is reasonably homogeneous on the nano-scale, and is rather similar to the silicoaluminophosphate analogue SAPO-34 (CHA) but different in nano-scale coking behavior compared to previously studied zeolite ZSM-5 (MFI).",

author = "Vreeswijk, \{S. H. van\} and M. Monai and R. Oord and Schmidt, \{J. E.\} and Vogt, \{E. T. C.\} and Poplawsky, \{J. D.\} and Weckhuysen, \{B. M.\}",

note = "Funding Information: This work is supported by the ARC-CBBC (Advanced Research Center – Chemical Building Blocks Consortium), which is cofounded and co-financed by the Netherlands Organisation for Scientific Research (NWO) and the Netherlands Ministry of Economic Affairs and Climate Policy, in collaboration with BASF. APT was conducted at ORNL's Center for Nanophase Materials Sciences (CNMS), which is a U.S. DOE Office of Science User Facility. The authors would like to thank James Burns (ORNL) for assistance in performing APT sample preparation and running the APT experiments. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

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doi = "10.1039/d1cy01938d",

language = "English",

volume = "12",

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AU - Vreeswijk, S. H. van

AU - Monai, M.

AU - Oord, R.

AU - Schmidt, J. E.

AU - Vogt, E. T. C.

AU - Poplawsky, J. D.

AU - Weckhuysen, B. M.

N1 - Funding Information: This work is supported by the ARC-CBBC (Advanced Research Center – Chemical Building Blocks Consortium), which is cofounded and co-financed by the Netherlands Organisation for Scientific Research (NWO) and the Netherlands Ministry of Economic Affairs and Climate Policy, in collaboration with BASF. APT was conducted at ORNL's Center for Nanophase Materials Sciences (CNMS), which is a U.S. DOE Office of Science User Facility. The authors would like to thank James Burns (ORNL) for assistance in performing APT sample preparation and running the APT experiments. Publisher Copyright: © The Royal Society of Chemistry.

PY - 2022/2/21

Y1 - 2022/2/21

N2 - The methanol-to-hydrocarbons (MTH) process, commonly catalyzed by zeolites, is of great commercial interest and therefore widely studied both in industry and academia. However, zeolite-based catalyst materials are notoriously hard to study at the nano-scale. Atom probe tomography (APT) is uniquely positioned among the suite of characterization techniques, as it can provide 3D chemical information with sub-nm resolution. In this work, we have used APT to study the nano-scale coking behavior of zeolite SSZ-13 and its relation to bulk coke formation on the macro-/micro-scale studied with operando and in situ UV-vis spectroscopy and microscopy. Radial distribution function analysis (RDF) of the APT data revealed short carbon–carbon length scale affinities, consistent with the formation of larger aromatic molecules (coke species). Using nearest neighbor distribution (NND) analysis, an increase in the homogeneity of carbon was found with increasing time-on-stream. However, carbon clusters could not be isolated due to spatial noise and limited clustering. Therefore, it was found that the coke formation in zeolite SSZ-13 (CHA) is reasonably homogeneous on the nano-scale, and is rather similar to the silicoaluminophosphate analogue SAPO-34 (CHA) but different in nano-scale coking behavior compared to previously studied zeolite ZSM-5 (MFI).

AB - The methanol-to-hydrocarbons (MTH) process, commonly catalyzed by zeolites, is of great commercial interest and therefore widely studied both in industry and academia. However, zeolite-based catalyst materials are notoriously hard to study at the nano-scale. Atom probe tomography (APT) is uniquely positioned among the suite of characterization techniques, as it can provide 3D chemical information with sub-nm resolution. In this work, we have used APT to study the nano-scale coking behavior of zeolite SSZ-13 and its relation to bulk coke formation on the macro-/micro-scale studied with operando and in situ UV-vis spectroscopy and microscopy. Radial distribution function analysis (RDF) of the APT data revealed short carbon–carbon length scale affinities, consistent with the formation of larger aromatic molecules (coke species). Using nearest neighbor distribution (NND) analysis, an increase in the homogeneity of carbon was found with increasing time-on-stream. However, carbon clusters could not be isolated due to spatial noise and limited clustering. Therefore, it was found that the coke formation in zeolite SSZ-13 (CHA) is reasonably homogeneous on the nano-scale, and is rather similar to the silicoaluminophosphate analogue SAPO-34 (CHA) but different in nano-scale coking behavior compared to previously studied zeolite ZSM-5 (MFI).

UR - https://www.scopus.com/pages/publications/85125744895

U2 - 10.1039/d1cy01938d

DO - 10.1039/d1cy01938d

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SN - 2044-4753

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SP - 1220

EP - 1228

JO - Catalysis Science & Technology

JF - Catalysis Science & Technology

IS - 4

ER -

Nano-scale insights regarding coke formation in zeolite SSZ-13 subject to the methanol-to-hydrocarbons reaction

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