Abstract
Micro- and nanoscale information on the activating and deactivating coking behaviour of zeolite catalyst materials increases our current understanding of many industrially applied processes, such as the methanol-to-hydrocarbon (MTH) reaction. Atom probe tomography (APT) was used to reveal the link between framework and coke elemental distributions in 3D with sub-nanometre resolution. APT revealed 10–20 nanometre-sized Al-rich regions and short-range ordering (within nanometres) between Al atoms. With confocal fluorescence microscopy, it was found that the morphology of the zeolite crystal as well as the secondary mesoporous structures have a great effect on the microscale coke distribution throughout individual zeolite crystals over time. Additionally, a nanoscale heterogeneous distribution of carbon as residue from the MTH reaction was determined with carbon-rich areas of tens of nanometres within the zeolite crystals. Lastly, a short length-scale affinity between C and Al atoms, as revealed by APT, indicates the formation of carbon-containing molecules next to the acidic sites in the zeolite.
| Original language | English |
|---|---|
| Article number | e202300094 |
| Journal | ChemPhysChem |
| Volume | 24 |
| Issue number | 13 |
| DOIs | |
| State | Published - Jul 3 2023 |
Funding
APT research was supported by the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. The authors would like to thank James Burns for assistance in performing APT sample preparation and running the APT experiments. Work was equally led by S.H. van Vreeswijk, J.D. Poplawsky and B.M. Weckhuysen. The research work was sponsored by the Netherlands Organisation for Scientific Research (NWO), Advanced Research Center – Chemical Building Blocks Consortium (ARC CBBC), as well as BASF in the form of a bilateral research project, the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation programme funded by the Ministry of Education, Culture and Science of the government of the Netherlands and the US Army Research Office (ARO). Nikos Nikolopoulos (UU) is acknowledged for taking the FIB‐SEM images.
| Funders | Funder number |
|---|---|
| ARC CBBC | |
| Advanced Research Center | |
| Center for Nanophase Materials Sciences | |
| Chemical Building Blocks Consortium | |
| MCEC | |
| Netherlands Center for Multiscale Catalytic Energy Conversion | |
| U.S. Department of Energy | |
| Army Research Office | |
| BASF | |
| Office of Science | |
| Oak Ridge National Laboratory | |
| Ministerie van Onderwijs, Cultuur en Wetenschap | |
| Nederlandse Organisatie voor Wetenschappelijk Onderzoek |
Keywords
- atom probe tomography
- coke formation
- confocal fluorescence microscopy
- methanol-to-hydrocarbons reaction
- zeolites