published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal.If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the "Taverne" license above, please follow below link for the End User

published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal.If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the "Taverne" license above, please follow below link for the End User

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.

No abstract

The hydrogenation of CO 2 to CH 3 OH is an important reaction for future renewable energy scenarios. Herein, we compare Cu/ZnO, Cu/CeO 2 , and Cu/ZnO–CeO 2 catalysts prepared by flame spray pyrolysis. The Cu loading and support composition were varied to understand the role of Cu–ZnO and Cu–CeO 2 interactions. CeO 2 addition improves Cu dispersion with respect to ZnO, owing to stronger Cu–CeO 2 interactions. The ternary Cu/ZnO–CeO 2 catalysts displayed a substantially higher CH 3 OH selectivity than binary Cu/CeO 2 and Cu/ZnO catalysts. The high CH 3 OH selectivity in comparison with a commercial Cu–ZnO catalyst is also confirmed for Cu/ZnO–CeO 2 catalyst prepared with high Cu loading (∼40 wt %). In situ IR spectroscopy was used to probe metal–support interactions in the reduced catalysts and to gain insight into CO 2 hydrogenation over the Cu–Zn–Ce oxide catalysts. The higher CH 3 OH selectivity can be explained by synergistic Cu–CeO 2 and Cu–ZnO interactions. Cu–ZnO interactions promote CO 2 hydrogenation to CH 3 OH by Zn-decorated Cu active sites. Cu–CeO 2 interactions inhibit the reverse water–gas shift reaction due to a high formate coverage of Cu and a high rate of hydrogenation of the CO intermediate to CH 3 OH. These insights emphasize the potential of fine-tuning metal–support interactions to develop improved Cu-based catalysts for CO 2 hydrogenation to CH 3 OH.