Abstract
Non-oxidative dehydroaromatization of methane (MDA) is a promising catalytic process for direct valorization of natural gas to liquid hydrocarbons. The application of this reaction in practical technology is hindered by a lack of understanding about the mechanism and nature of the active sites in benchmark zeolite-based Mo/ZSM-5 catalysts, which precludes the solution of problems such as rapid catalyst deactivation. By applying spectroscopy and microscopy, it is shown that the active centers in Mo/ZSM-5 are partially reduced single-atom Mo sites stabilized by the zeolite framework. By combining a pulse reaction technique with isotope labeling of methane, MDA is shown to be governed by a hydrocarbon pool mechanism in which benzene is derived from secondary reactions of confined polyaromatic carbon species with the initial products of methane activation.
| Original language | English |
|---|---|
| Pages (from-to) | 1016-1020 |
| Number of pages | 5 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 57 |
| Issue number | 4 |
| DOIs | |
| Publication status | Published - 22 Jan 2018 |
Funding
Financial support from the SABIC-NWO CATC1CHEM CHIPP project is gratefully acknowledged. M.V.F. would like to thank the Russian Science Foundation (14-13-00826) for supporting the EPR studies. A.S.P. would like to thank FASO (0333-2016-0001). The authors thank Dr. Frans Tichelaar (TU Delft) for assistance with TEM analysis and Dr. Alessandro Longo for assistance with XAS experiments. We thank Dr. Christoph Dittrich (SABIC), Dr. Frank Mostert (SABIC), Dr. Xander Nijhuis (SABIC), Prof. Dr. Freek Kapteijn (TU Delft), Prof. Dr. Jorge Gascon (TU Delft), and Ina Vollmer (TU Delft) for fruitful discussion. We thank Kira Vranken for the design of cover image.
Keywords
- dehydroaromatization
- hydrocarbons
- methane
- Mo/ZSM-5
- organocatalysis